CN104151549A - Polyimide resin adopting thermosetting comb type structure and preparation method thereof - Google Patents
Polyimide resin adopting thermosetting comb type structure and preparation method thereof Download PDFInfo
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- CN104151549A CN104151549A CN201410379856.4A CN201410379856A CN104151549A CN 104151549 A CN104151549 A CN 104151549A CN 201410379856 A CN201410379856 A CN 201410379856A CN 104151549 A CN104151549 A CN 104151549A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 55
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 150000008065 acid anhydrides Chemical class 0.000 claims description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- NDWKKKBYNUUHKJ-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C1=CC=CC=C1)=O.C1(=CC=CC=C1)C#C Chemical compound C(C1=CC=CC=C1)(=O)OC(C1=CC=CC=C1)=O.C1(=CC=CC=C1)C#C NDWKKKBYNUUHKJ-UHFFFAOYSA-N 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 8
- CSNFMBGHUOSBFU-UHFFFAOYSA-N pyrimidine-2,4,5-triamine Chemical group NC1=NC=C(N)C(N)=N1 CSNFMBGHUOSBFU-UHFFFAOYSA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- -1 naphthalene acetylene anhydride Chemical class 0.000 description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- APXBXAJWVZTKSE-UHFFFAOYSA-N pyridine-2,3,4-triamine Chemical compound NC1=CC=NC(N)=C1N APXBXAJWVZTKSE-UHFFFAOYSA-N 0.000 description 2
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- WWEWYHLJEWDHLY-UHFFFAOYSA-N C(=C)C1=C(C(=CC(=C1)N)N)C=CC1=CC=CC=C1 Chemical compound C(=C)C1=C(C(=CC(=C1)N)N)C=CC1=CC=CC=C1 WWEWYHLJEWDHLY-UHFFFAOYSA-N 0.000 description 1
- MITOOYSZNBJNHQ-UHFFFAOYSA-N Cc(cc1)ccc1Oc1cc(C)c(C)cc1 Chemical compound Cc(cc1)ccc1Oc1cc(C)c(C)cc1 MITOOYSZNBJNHQ-UHFFFAOYSA-N 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N Cc1c(C)c(C)ncc1 Chemical compound Cc1c(C)c(C)ncc1 HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- DHEHMSXIMBXYIC-UHFFFAOYSA-N Cc1cc2c(C)nc(C)nc2cc1 Chemical compound Cc1cc2c(C)nc(C)nc2cc1 DHEHMSXIMBXYIC-UHFFFAOYSA-N 0.000 description 1
- HCATUIMBJIDQDT-UHFFFAOYSA-N Cc1nc(C)nc(C)c1 Chemical compound Cc1nc(C)nc(C)c1 HCATUIMBJIDQDT-UHFFFAOYSA-N 0.000 description 1
- 241001274660 Modulus Species 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides polyimide resin adopting a thermosetting comb type structure and a preparation method thereof and aims at solving the problems that the thermosetting polyimide resin in the prior art is single in structure, poor in processing property, higher in price, and the like. The preparation method of the polyimide resin adopting the thermosetting comb type structure mainly comprises the steps as follows: firstly, mixing and resolving; secondly, synthesizing a comb type unit; thirdly, polymerizing; fourthly, obtaining the polyimide resin adopting the thermosetting comb type structure through a density adjusting process. The preparation method is mainly used for preparing the polyimide resin adopting the thermosetting comb type structure; the polyimide resin is simple in synthesis process, better in composite material processing property, longer in storage period, higher in physical-chemical property, has wide application prospect in areas such as high-temperature resistance fiber composite material, and moreover is reasonable in synthesis route, easy to obtain raw material, relatively lower in price, simple in synthesis technology, and has important popularization and application value.
Description
Technical field
That the present invention relates to is the preparation method, particularly fire resistant resin and preparation method thereof of resin matrix and 0 for a kind of fibre composite.
Background technology
Polyimide (PI) refers to a base polymer that contains imide ring on main chain.As far back as 1908, just have been reported, but until the mid-40 in 20th century just has some patent documentations (US2710853) to occur, but really as a kind of macromolecular material, develop and start from the fifties.E.I.Du Pont Company had applied for a series of patents at that time, and in the mid-1960s, first, by Kapton (Kapton) and varnish (Pyre ML) commercialization, had started thus the epoch that polyimide is flourish.Imide structure is:
Polyimide, because having excellent high temperature resistant, high strength, high-modulus, high tenacity and insulating property etc., becomes important structured material and the polymeric film material in the fields such as space flight and aviation and microelectronics.But, due to thermoplastic polyimide conventionally show high melt viscosity and in organic solvent poor solvability, while making them manufacture matrix material and tackiness agent by methods such as compression molding, injection moldings, often there is very large difficulty.The problem that is difficult to processing in order to solve the high melt viscosity, low-solubility etc. of high-performance polymer, the heat cured polyimide exploitation of the performed polymer that contains reactive group has caused people's extensive concern.This method adopts can introduce reactive group as crosslinked precursor on processing structure to lower molecular weight performed polymer or thermoplasticity, and the excellent processability that utilizes this class to be cross-linked precursor makes its crosslinking curing become temperature high performance high thermosetting material after processing again.Because this method is by organic unified having arrived in the middle of commaterial of the good machinery of the processing characteristics of thermoplastic material excellence and thermosetting material and thermal characteristics, more and more received in the last few years developing material persons' concern.But at present thermoset polyimide resin still exists resin viscosity larger, and the widespread use of problem the limited thermoset polyimide resin such as resin cured matter toughness is poor.
Summary of the invention
The object of the present invention is to provide a kind of thermoset comb-type structure polyimide resin with good mechanical property, resistance toheat.The present invention also aims to provide the preparation method that a kind of technical process is simple, be applicable to the thermoset comb-type structure polyimide resin of suitability for industrialized production.
Thermoset comb-type structure polyimide resin of the present invention has following structural formula:
Wherein: the integer of N >=1;
R
1a kind of in the isomers of following several structures and each structure,
R
2a kind of in the isomers of following several structures and each structure,
A is a kind of in the isomers of following several structure and each structure:
The preparation method of thermoset comb-type structure polyimide resin of the present invention is:
Step 1, mixed dissolution: polymerizable acid anhydrides being placed in to container, adding ethanol, is that 80 ℃～200 ℃, stirring and refluxing are to completely dissolving and obtain polymerizable acid anhydride solution in temperature; Dibasic acid anhydride being placed in to container, adding ethanol, is 80 ℃～200 ℃ in temperature, and stirring and refluxing is to completely dissolving and obtain dibasic acid anhydride solution; Ternary ammonia is placed in to container, adds ethanol, obtain ternary cholamine solution;
Step 2, comb type unit synthetic: the ternary cholamine that step 1 is obtained is dissolved under the condition of stirring constant temperature to 80 ℃～200 ℃; In 0.5～12 hour, drip the polymerizable acid anhydride solution that step 1 obtains, in polymerizable acid anhydride solution, in polymerizable acid anhydrides and ternary cholamine solution, the mass ratio of ternary ammonia is 0.5～10:1, continue constant temperature to 80 ℃～200 ℃ back flow reaction 0.5～12 hour, the speed of 0.5-5 ℃/min is cooled to the ethanolic soln that room temperature obtains comb type unit;
Step 3, polymerization: by the ethanolic soln of the resulting comb type of step 2 unit constant temperature to 80 ℃～200 ℃ under agitation condition; In 0.5～12 hour, drip the dibasic acid anhydride solution that step 1 obtains, in dibasic acid anhydride solution, in dibasic acid anhydride and ternary cholamine solution, the mass ratio of ternary ammonia is 0.5～10:1; Continue constant temperature to 80 ℃～200 ℃ back flow reaction 0.5～12 hour; In 0.5～12 hour, drip the polymerizable acid anhydride solution that step 1 obtains, in dibasic acid anhydride solution, in polymerizable acid anhydrides and ternary cholamine solution, the mass ratio of ternary ammonia is 0.05～1:1; Continue constant temperature to 80 ℃～200 ℃ of back flow reaction and within 0.5～12 hour, obtain comb-shaped polymer ethanolic soln;
Step 4, concentration adjustment: by the underpressure distillation 0.5～12 hour under the condition of 80 ℃～200 ℃ of stirrings ,-0.03～-0.09MPa, constant temperature of the resulting comb-shaped polymer ethanolic soln of step 3, then be warming up to and under the condition of 80 ℃～200 ℃ ,-0.03～-0.09MPa, continue underpressure distillation to soltion viscosity and reach 100～100000mPaS, the speed of 0.5-5 ℃/min is cooled to room temperature and obtains thermoset comb-type structure polyimide resin.
In step 1, ethanol and polymerizable acid anhydrides mass ratio are 1～10:1; Ethanol and dibasic acid anhydride mass ratio are 1～10:1; Ethanol and ternary ammonia mass ratio are 1～10:1.
The stirring velocity stirring described in each step is 500 revs/min～2500 revs/min.
The present invention will solve the problems such as the poor and toughness of existing polyimide resin manufacturability is poor, and a kind of technical process proposing is simple, be applicable to suitability for industrialized production, and have polyimide resin of good mechanical property, resistance toheat and processing performance and preparation method thereof.
Advantage of the present invention is mainly reflected in: one, a kind of thermoset comb-type structure of the present invention polyimide resin solves the poor shortcoming of current polyimide resin manufacturability; Two, to have synthesis technique simple for a kind of thermoset comb-type structure of the present invention polyimide resin, preparation composite technology better performances, the advantage such as storage period is long; Three, a kind of thermoset comb-type structure of the present invention polyimide resin has higher physicochemical property, in high-temperature fibre prepare composite, has broad application prospects; Four, synthetic line of the present invention is reasonable, raw material is easy to get, price is relatively cheap and synthesis technique is simple, has important promotion and application and is worth.
Accompanying drawing explanation
Fig. 1 is poor formula scanning calorimetric analysis (DSC) collection of illustrative plates of the polyimide resin of test one preparation;
Fig. 2 is infrared spectra (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 is solidified;
Fig. 4 is H nucleus magnetic resonance (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.
Embodiment
For example the present invention is described in more detail below.
Embodiment one:
A kind of for in phenylacetylene benzoic anhydride, naphthalene acetylene anhydride, phenylacetylene anhydride naphthalene, naphthalene acetylene naphthalene acid anhydride etc. of polymerizable acid anhydrides described in present embodiment.
Ternary ammonia described in present embodiment is Triaminopyrimidine, triamino pyridine, triaminobenzene, triamino phenyl ether ,-triaminotriphenyl-methane, quinazoline triamine, 2-vinyl-4, a kind of in 6-diamino-1,3,5-triazines etc.
Dibasic acid anhydride described in present embodiment is a kind of in pyromellitic dianhydride, biphenyl tetracarboxylic acid anhydrides, benzophenone tetracarboxylic dianhydride, diphenyl ether tetraformic dianhydride etc.
A kind of thermoset comb-type structure polyimide resin described in present embodiment solves the poor shortcoming of current polyimide resin manufacturability.
The advantages such as it is simple that a kind of thermoset comb-type structure polyimide resin described in present embodiment has synthesis technique, prepares composite technology better performances, and storage period is long.
A kind of thermoset comb-type structure polyimide resin described in present embodiment has higher physicochemical property, in high-temperature fibre prepare composite, has broad application prospects.
A kind of thermoset comb-type structure polyimide resin synthetic line described in present embodiment rationally, raw material is easy to get, price is relatively cheap and synthesis technique is simple, has important promotion and application and be worth.
Specifically complete according to the following steps:
One, mixed dissolution: polymerizable acid anhydrides is placed in to flask, add ethanol, ethanol and polymerizable acid anhydrides mass ratio are (1～10:1), in temperature, are that 80 ℃～200 ℃, stirring velocity are that stirring and refluxing under the condition of 500 revs/min～2500 revs/min is to completely dissolving and obtain polymerizable acid anhydride solution; Dibasic acid anhydride is placed in to flask, add ethanol, ethanol and binary are closed acid anhydrides mass ratio for (1～10:1), in temperature, are that 80 ℃～200 ℃, stirring velocity are that stirring and refluxing under the condition of 500 revs/min～2500 revs/min is to completely dissolving and obtain dibasic acid anhydride solution; Ternary ammonia is placed in to flask, adds ethanol, ethanol and ternary ammonia mass ratio are (1～10:1), obtain ternary cholamine solution.Two, comb type unit is synthetic: it is constant temperature to 80 ℃ under the condition of 500 revs/min～2500 revs/min～200 ℃ that the ternary cholamine that step 1 is obtained is dissolved in stirring velocity; In 0.5～12 hour, drip the polymerizable acid anhydride solution that step 1 obtains, in polymerizable acid anhydride solution, in polymerizable acid anhydrides and ternary cholamine solution, the mass ratio of ternary ammonia is (0.5～10:1), continue constant temperature to 80 ℃～200 ℃ back flow reaction 0.5～12 hour, the speed of 0.5-5 ℃/min is cooled to the ethanolic soln that room temperature obtains comb type unit; Three, polymerization: be constant temperature to 80 ℃ under the condition of 500 revs/min～2500 revs/min～200 ℃ by the ethanolic soln low whipping speed of the resulting comb type of step 2 unit; In 0.5～12 hour, drip the dibasic acid anhydride solution that step 1 obtains, in dibasic acid anhydride solution, in dibasic acid anhydride and ternary cholamine solution, the mass ratio of ternary ammonia is (0.5～10:1); Continue constant temperature to 80 ℃～200 ℃ back flow reaction 0.5～12 hour; In 0.5～12 hour, drip the polymerizable acid anhydrides R2 solution that step 1 obtains, in dibasic acid anhydride solution, in polymerizable acid anhydrides and ternary cholamine solution, the mass ratio of ternary ammonia is (0.05～1:1); Continue constant temperature to 80 ℃～200 ℃ of back flow reaction and within 0.5～12 hour, obtain comb-shaped polymer ethanolic soln; Four, concentration adjustment: be 500 revs/min～2500 revs/min by the resulting comb-shaped polymer ethanolic soln of step 3 low whipping speed,-0.03～-0.09MPa, under the condition that constant temperature is 80 ℃～200 ℃, underpressure distillation is 0.5～12 hour, then be warming up to 80 ℃～200 ℃,-0.03～-0.09MPa condition under continue underpressure distillation to soltion viscosity and reach 100～100000mPaS, the speed of 0.5-5 ℃/min is cooled to room temperature and obtains thermoset comb-type structure polyimide resin.
A kind of thermoset comb-type structure polyimide resin described in present embodiment solves the poor shortcoming of current polyimide resin manufacturability.
The advantages such as it is simple that a kind of thermoset comb-type structure polyimide resin described in present embodiment has synthesis technique, prepares composite technology better performances, and storage period is long.
A kind of thermoset comb-type structure polyimide resin described in present embodiment has higher physicochemical property, in high-temperature fibre prepare composite, has broad application prospects.
A kind of thermoset comb-type structure polyimide resin synthetic line described in present embodiment rationally, raw material is easy to get, price is relatively cheap and synthesis technique is simple, has important promotion and application and be worth.
Embodiment two: present embodiment is different from embodiment one: the polymerizable acid anhydrides described in step 1 is one or more mixtures in phenylacetylene benzoic anhydride, naphthalene acetylene anhydride, phenylacetylene anhydride naphthalene, naphthalene acetylene naphthalene acid anhydride etc.Other are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: the ternary ammonia described in step 2 is Triaminopyrimidine, triamino pyridine, triaminobenzene, triamino phenyl ether ,-triaminotriphenyl-methane, quinazoline triamine, 2-vinyl-4,6-diaminostilbene, one or more mixtures in 3,5-triazine etc.He is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: dibasic acid anhydride described in step 3 is one or more mixtures in pyromellitic dianhydride, biphenyl tetracarboxylic acid anhydrides, benzophenone tetracarboxylic dianhydride, diphenyl ether tetraformic dianhydride etc.Other are identical with one of embodiment two to four.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of cyanate prepreg, specifically completes according to the following steps:
One, mixed dissolution: phenylacetylene benzoic anhydride is placed in to flask, adds ethanol, ethanol and phenylacetylene benzoic anhydride mass ratio are 5:1 is that 80 ℃, stirring velocity are that stirring and refluxing under the condition of 1500 revs/min is to completely dissolving and obtain phenylacetylene benzoic anhydride solution in temperature; By in bibenzene tetracarboxylic dianhydride flask, add ethanol, ethanol and bibenzene tetracarboxylic dianhydride mass ratio are 5:1, in temperature, are that 80 ℃, stirring velocity are that stirring and refluxing under the condition of 1500 revs/min is to completely dissolving and obtain bibenzene tetracarboxylic dianhydride solution; Triaminopyrimidine is placed in to flask, adds ethanol, ethanol and ternary ammonia mass ratio are 3:1, obtain Triaminopyrimidine ethanolic soln.Two, comb type unit is synthetic: it is constant temperature to 100 ℃ under the condition of 1500 revs/min that the Triaminopyrimidine ethanol that step 1 is obtained is dissolved in stirring velocity; In 1 hour, drip the phenylacetylene benzoic anhydride solution that step 1 obtains, in phenylacetylene benzoic anhydride solution in phenylacetylene benzoic anhydride and Triaminopyrimidine solution the amount of substance of Triaminopyrimidine than being 1:3, continue constant temperature to 80 ℃ back flow reaction 2 hours, the speed of 3 ℃/min is cooled to the ethanolic soln that room temperature obtains comb type unit; Three, polymerization: be constant temperature to 80 ℃ under the condition of 1500 revs/min by the ethanolic soln low whipping speed of the resulting comb type of step 2 unit; In 1 hour, drip the bibenzene tetracarboxylic dianhydride solution that step 1 obtains, in bibenzene tetracarboxylic dianhydride solution, in bibenzene tetracarboxylic dianhydride and ternary cholamine solution, the mass ratio of ternary ammonia is 4:5; Continue constant temperature to 100 ℃ back flow reaction 2 hours; In 0.5 hour, drip the phenylacetylene benzoic anhydride solution that step 1 obtains, in phenylacetylene benzoic anhydride solution in phenylacetylene benzoic anhydride solution and Triaminopyrimidine ethanolic soln the amount of substance of ternary ammonia than being 2:5; Continue constant temperature to 80 ℃ back flow reaction and within 4 hours, obtain comb-shaped polymer ethanolic soln; Four, concentration adjustment: be 1500 revs/min by the resulting comb-shaped polymer ethanolic soln of step 3 low whipping speed,-0.03～-0.09MPa, under the condition that constant temperature is 80 ℃, underpressure distillation is 2 hours, then be warming up to 120 ℃,-0.03～-0.09MPa condition under continue underpressure distillation to soltion viscosity and reach 100～100000mPaS, the speed of 5 ℃/min is cooled to room temperature and obtains thermoset comb-type structure polyimide resin.
Adopt poor formula scanning amount thermal analyzer (DSC) to detect the polyimide resin of this test one preparation, detected result as shown in Figure 1, Fig. 1 is poor formula scanning calorimetric analysis (DSC) collection of illustrative plates of the polyimide resin of test one preparation, can see in figure only 350 ℃ of exothermic peaks that come into existence, illustrate that polyimide resin starts to occur cross-linking and curing reaction 350 ℃ of left and right.
Adopt infrared spectra (IR) to detect the polyimide resin of this test one preparation, detected result as shown in Figure 2, Fig. 2 is infrared spectra (IR) collection of illustrative plates of the polyimide resin of test one preparation, can see synthetic test one preparation polyimide resin polyimide (BPMR) although and some peak type of the infared spectrum of KH370 slightly different, but the position at peak is basic identical, illustrate that BPMR has the similar polyimide structures with KH370.
Adopt thermal weight loss (TG) to detect the polyimide resin after solidifying of this test one preparation, detected result as shown in Figure 3, Fig. 3 is thermal weight loss (TG) collection of illustrative plates of the polyimide resin after test one is solidified, result shows that polyimide resin heat decomposition temperature after solidifying of this test one preparation is higher than 500 ℃, 5% thermal weight loss temperature is 530 ℃, and 800 ℃ of thermal weight losses are 35.76%.
Adopt H nucleus magnetic resonance (NMR) to detect the polyimide resin of this test one preparation, detected result as shown in Figure 4.
Adopt dynamic thermal analysis (DMA) to detect the polyimide resin of this test one preparation, detected result as shown in Figure 5, Fig. 5 is dynamic thermal analysis (DMA) collection of illustrative plates of the polyimide resin of test one preparation, 10 ℃/min of temperature rise rate, DMA result shows that resin glass transition temperature is about 396 ℃, higher than the polyimide II generation (371 ℃) of NASA.Before 350 ℃ of resin storage moduluss (E '), without considerable change, illustrate that resin can be used at 350 ℃.
Claims (4)
1. a thermoset comb-type structure polyimide resin, is characterized in that having following structural formula:
Wherein: the integer of N >=1;
R
1a kind of in the isomers of following several structures and each structure,
R
2a kind of in the isomers of following several structures and each structure,
A is a kind of in the isomers of following several structure and each structure:
2. a preparation method for thermoset comb-type structure polyimide resin as claimed in claim 1, is characterized in that:
Step 1, mixed dissolution: polymerizable acid anhydrides being placed in to container, adding ethanol, is that 80 ℃～200 ℃, stirring and refluxing are to completely dissolving and obtain polymerizable acid anhydride solution in temperature; Dibasic acid anhydride being placed in to container, adding ethanol, is 80 ℃～200 ℃ in temperature, and stirring and refluxing is to completely dissolving and obtain dibasic acid anhydride solution; Ternary ammonia is placed in to container, adds ethanol, obtain ternary cholamine solution;
Step 2, comb type unit synthetic: the ternary cholamine that step 1 is obtained is dissolved under the condition of stirring constant temperature to 80 ℃～200 ℃; In 0.5～12 hour, drip the polymerizable acid anhydride solution that step 1 obtains, in polymerizable acid anhydride solution, in polymerizable acid anhydrides and ternary cholamine solution, the mass ratio of ternary ammonia is 0.5～10:1, continue constant temperature to 80 ℃～200 ℃ back flow reaction 0.5～12 hour, the speed of 0.5-5 ℃/min is cooled to the ethanolic soln that room temperature obtains comb type unit;
Step 3, polymerization: by the ethanolic soln of the resulting comb type of step 2 unit constant temperature to 80 ℃～200 ℃ under agitation condition; In 0.5～12 hour, drip the dibasic acid anhydride solution that step 1 obtains, in dibasic acid anhydride solution, in dibasic acid anhydride and ternary cholamine solution, the mass ratio of ternary ammonia is 0.5～10:1; Continue constant temperature to 80 ℃～200 ℃ back flow reaction 0.5～12 hour; In 0.5～12 hour, drip the polymerizable acid anhydride solution that step 1 obtains, in dibasic acid anhydride solution, in polymerizable acid anhydrides and ternary cholamine solution, the mass ratio of ternary ammonia is 0.05～1:1; Continue constant temperature to 80 ℃～200 ℃ of back flow reaction and within 0.5～12 hour, obtain comb-shaped polymer ethanolic soln;
Step 4, concentration adjustment: by the underpressure distillation 0.5～12 hour under the condition of 80 ℃～200 ℃ of stirrings ,-0.03～-0.09MPa, constant temperature of the resulting comb-shaped polymer ethanolic soln of step 3, then be warming up to and under the condition of 80 ℃～200 ℃ ,-0.03～-0.09MPa, continue underpressure distillation to soltion viscosity and reach 100～100000mPaS, the speed of 0.5-5 ℃/min is cooled to room temperature and obtains thermoset comb-type structure polyimide resin.
3. the preparation method of thermoset comb-type structure polyimide resin according to claim 2, is characterized in that: in step 1, ethanol and polymerizable acid anhydrides mass ratio are 1～10:1; Ethanol and dibasic acid anhydride mass ratio are 1～10:1; Ethanol and ternary ammonia mass ratio are 1～10:1.
4. according to the preparation method of the thermoset comb-type structure polyimide resin described in claim 2 or 3, it is characterized in that: the stirring velocity stirring described in each step is 500 revs/min～2500 revs/min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20040006196A1 (en) * | 2002-03-26 | 2004-01-08 | Scola Daniel A. | 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 |
| CN101265227A (en) * | 2008-04-25 | 2008-09-17 | 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 |
-
2014
- 2014-08-04 CN CN201410379856.4A patent/CN104151549B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20040006196A1 (en) * | 2002-03-26 | 2004-01-08 | Scola Daniel A. | 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 |
| CN101265227A (en) * | 2008-04-25 | 2008-09-17 | 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 |
Non-Patent Citations (3)
| Title |
|---|
| XIAOMEI FANG ET AL.: "A Study of the Kinetics of the Microwave Cure of a Phenylethynyl-Terminated Imide Model Compound and Imide Oligomer (PETI-5)", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
| 刘燕峰等: "含苯乙炔基的酰亚胺低聚物及其复合材料研究", 《热固性树脂》 * |
| 杨明等: "耐高温交联侧基苯乙炔封端酰亚胺预聚体", 《高等学校化学学报》 * |
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