CN103834008A - Novel phthalonitrile resin and preparation method thereof - Google Patents
Novel phthalonitrile resin and preparation method thereof Download PDFInfo
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- CN103834008A CN103834008A CN201410085565.4A CN201410085565A CN103834008A CN 103834008 A CN103834008 A CN 103834008A CN 201410085565 A CN201410085565 A CN 201410085565A CN 103834008 A CN103834008 A CN 103834008A
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- 0 Cc(cc1)ccc1C(c1ccc(C)cc1)=* Chemical compound Cc(cc1)ccc1C(c1ccc(C)cc1)=* 0.000 description 5
- YLYGJDUBXATBCZ-UHFFFAOYSA-N CCC(C)(c1ccc(C)cc1)c1ccc(C)cc1 Chemical compound CCC(C)(c1ccc(C)cc1)c1ccc(C)cc1 YLYGJDUBXATBCZ-UHFFFAOYSA-N 0.000 description 1
- WECJUPODCKXNQK-UHFFFAOYSA-N COc1ccc(Cc(cc2)ccc2OC)cc1 Chemical compound COc1ccc(Cc(cc2)ccc2OC)cc1 WECJUPODCKXNQK-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a novel phthalonitrile resin and a preparation method thereof. Compared with a conventional phthalonitrile resin (only 4-nitro phthalonitrile as an end-capping reagent, the novel phthalonitrile resin is introduced with 3-nitro novel phthalonitrile resin to cooperate end capping, and thus the asymmetry of a resin structure is increased and the turbidity of a resin component is increased (see a formula 1). Compared with the conventional phthalonitrile resin, the novel phthalonitrile resin disclosed by the invention has the characteristics of low melting temperature, good solubility, wide processing window, low curing temperature and the like; a prepared resin molded part and a resin-based composite material are low in porosity, excellent heat-resistant quality, and high in mechanical property, and can be applied to the fields of aerospace, a space technology, machine manufacturing, and the like as a light-weight and high-temperature resistant part. The formula is described in the specification.
Description
Technical field
The present invention relates to a kind of thermoset o-phthalonitrile resin and preparation method thereof
Background technology
Polymer matrix composites (Resin Matrix Composite) are class matrix materials of current technology comparative maturity and widespread use.The starting material of polymer matrix composites, comprise matrix phase and wild phase and additive.Matrix phase material refers to the various polymkeric substance as matrix, comprises thermosetting resin and thermoplastic resin, and wild phase refers to various fibers, as glass fibre, carbon fiber, aramid fiber, hdpe fiber etc.
The thermoset substrate resin of polymer matrix composites mainly comprises epoxy resin, bismaleimide resin and polyimide resin three major types, wherein only has the temperature resistant grade of polyimide can meet and exceed 300 DEG C.O-phthalonitrile resin is the another kind of resin system that temperature resistant grade exceedes 300 DEG C that is considered to.
From eighties of last century eighties, the phthalonitrile monomer of various structures is synthesized out, it is synthetic substantially all as shown in reaction formula 1, under the catalysis of Anhydrous potassium carbonate, generated the bis-phthalonitrile monomer of two ends sealed by 4-nitrophthalonitrile and dihydric phenol, reaction is generally at N, in the intensive polar solvents such as dinethylformamide (DMF) or N,N-dimethylacetamide (DMAc), carry out, temperature of reaction is from 80 DEG C to 140 DEG C.
The synthetic route of reaction formula 1 bis-phthalonitrile monomer
O-phthalonitrile resin system has excellent resistance to elevated temperatures, and its heat resisting temperature can be up to 350 DEG C, and even 450 DEG C still do not have clear and definite second-order transition temperature.O-phthalonitrile resin is addition curing, and solidification process does not have small molecules to discharge, and porosity is low, mechanical property excellence.Research shows phthalonitrile/carbon-fibre composite and traditional application performance, and preferably polyimide resin PMR-15 composite property is suitable, even slightly excellent, thereby likely as lightweight, high-temperature-resistant structure parts, in field application such as aerospace, space technology, machinofacture.In addition, the feature such as phthalonitrile cured article also has low water absorption, fire-retardant fireproof excellent performance, likely applies in field, naval vessel.
But, problem of o-phthalonitrile resin ubiquity, fusing point is higher, and melt temperature and the processing characteristics of monomer are closely related, and the higher meeting of melt temperature causes the process window of resin narrower, poor processability.According to the report of document, the relation of various monomer structures and fusing point is as shown in table 1.
The fusing point of the various structure phthalonitrile monomers of table 1
As can be seen from Table 1, phthalonitrile monomer all has higher fusing point, approaches or exceedes 200 DEG C, has brought certain inconvenience to forming process.Foreign scholar studies the fusing point of more biphenyl structural phthalonitrile monomer especially up to 230 DEG C, and after catalyzer blend, the process window of resin system is narrower.Based on this, foreign scholar starts to reduce the fusing point of phthalonitrile monomer, has synthesized the monomer that between a series of capping groups, abutment segment is grown, in table 2.
Table 2 contains compared with phthalonitrile monomer structure and the melt temperature interval of long-chain joint
In table, listed molecular backbone chain has certain length, the degree of crystallinity of molecule reduces gradually, likely become noncrystalline state, fusing point or Tg are also reduced to 100 DEG C of left and right, even lower, brought certain facility to machine-shaping, but longer segment needs higher solidification value just can reach the thermal characteristics of short chain section resin cured matter, short chain section solidification value is up to 375 DEG C, and long-chain section often need to be up to 425 DEG C.
The present invention is first by 3-nitro-1,2-phthalonitrile (3-nitrophthalonitrile) is introduced resin system, and with 4-nitro-1,2-phthalonitrile (4-nitrophthalonitrile) is collaborative as capping group, and the phthalonitrile-terminated group of contraposition phthalonitrile and a position is along with the difference of feed ratio can regulate arbitrarily.Between the introducing of the phthalonitrile-terminated group in position increased the asymmetry of molecular structure, increased the randomness of resin composition simultaneously, effectively reduce the fusing point of o-phthalonitrile resin, improved the solubleness of resin, greatly improved the process industrial art performance of o-phthalonitrile resin.And through experimental verification, the introducing of a position phthalonitrile structure does not reduce resistance toheat and the mechanical property of resin.
Summary of the invention
The object of the present invention is to provide a kind of o-phthalonitrile resin of novel hot setting low melting point.
Another object of the present invention is to provide a kind of method of preparing above-mentioned matrix resin.
The present invention is achieved through the following technical solutions:
A kind of o-phthalonitrile resin, is characterized in that, described resin is selected from the mixture as shown in the formula three kinds of polymkeric substance shown in (1), formula (2) or formula (3).
Wherein, n
1, n
2, n
3be selected from independently of one another the integer of 0-4;
R in various
1be selected from independently of one another
R
2be selected from independently of one another
R
3be selected from independently of one another
According to the present invention, in described mixture, the mol ratio of formula (1), formula (2) and formula (3) is (20-45): (40-60): (10-25), and preferably (25-40): (45-55): (12-20), be more preferably 36:49:15.
According to the present invention, preferably, R in formula (1)
1with R in formula (2) and formula (3)
1for same structure; Or R in formula (1)
2with R in formula (2) and formula (3)
2for same structure; Or, R in formula (1)
3with R in formula (2) and formula (3)
3for same structure.Due to the R in each component structure in mixture
1and R
2determined by raw material, once raw material is definite, the R in different molecular structures
1and R
2be fixed sturcture.
According to the preferred technical solution of the present invention, the mixture of wherein said resin is selected from:
Or, be selected from:
Or, be selected from:
Or, be selected from:
Or, be selected from:
The present invention also provides the preparation method of above-mentioned o-phthalonitrile resin, it is characterized in that, described step comprises:
After described phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, slowly be added drop-wise in the solution of the aromatic dicarboxylic phenol that is dissolved in organic solvent and optional aromatic dicarboxylic halogenated compound, under the condition of catalyzer and optional dewatering agent, o-phthalonitrile resin is prepared in reaction.
Wherein, R1, R2, R3, n1, n2, the definition of n3 is as defined above.
Preferably,
Work as n1, n2, when n3=0, after phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, slowly be added drop-wise in the aromatic dicarboxylic phenol solution being dissolved in organic solvent the mixture of reaction preparation o-phthalonitrile resin of the present invention under catalyzer and optional dewatering agent condition.Or,
Work as n1, n2, when the integer of n3=1-4, after described phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, slowly be added drop-wise in the aromatic dicarboxylic phenol and aromatic dicarboxylic halogenated compound solution being dissolved in organic solvent, under catalyzer and optional dewatering agent condition, o-phthalonitrile resin is prepared in reaction.
According to the present invention, described phthalonitrile-terminated dose is selected from 3-nitro-1,2-phthalonitrile or 3-nitro-1,2-phthalonitrile and 4-nitro-1, the mixture of 2-phthalonitrile.
According to the present invention, described aromatic dicarboxylic phenol is pyrocatechol, Resorcinol, and Resorcinol, 4,4'-'-biphenyl diphenol, 4,4'-dioxydiphenyl methane, dihydroxyphenyl propane, 6F dihydroxyphenyl propane, containing a kind of in polyimide structures dihydric phenol or the mixture of any two kinds wherein.
According to the present invention, described aromatic dicarboxylic halogenated compound is 4,4 '-difluoro benzophenone, isophthalic dibromo, two (4-fluorophenyl) phenyl phosphine oxide, a kind of in 4,4'-dichloro diphenyl sulfone or the wherein mixture of any two kinds.
According to the present invention, the molfraction ratio of described aromatic dicarboxylic phenol, aromatic dicarboxylic halogenated compound and O-phthalic itrile group end-capping reagent is: (n+1): n:2, and wherein n=0-4, n comprises n1, n2, n3 any one.
The method according to this invention, described organic solvent is DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone, or it mixes arbitrarily.
Preferably, aromatic dicarboxylic phenol is with the molfraction of described organic solvent than being 1:11.7-37.2, and aromatic dicarboxylic halogenated compound is 1:10.6-24.8 with the molfraction ratio of described organic solvent.
Described catalyzer is that Anhydrous potassium carbonate, anhydrous sodium carbonate, potassium hydroxide, sodium hydroxide or its mix arbitrarily; Described dewatering agent is the mixture of cuprous iodide and phenanthrolene.
Preferably, described aromatic dicarboxylic phenol and optional aromatic dicarboxylic halogenated compound at room temperature, are dissolved in organic solvent under protection of inert gas.
Preferably, described method comprises: at described aromatic dicarboxylic phenol and optional aromatic dicarboxylic halogenated compound under room temperature (5-30 DEG C), under protection of inert gas, be dissolved in organic solvent in after, add catalyzer, and be warming up to 50-130 DEG C.
Preferably, described method be also included in above-mentioned reaction complete after, make reaction system insulation reaction 5-12 hour, preferably 6-10 hour.
Also more preferably, after insulation reaction, reaction system is cooled to room temperature, solution system is deposited in several times distilled water or acidic aqueous solution, filter and obtain product.Also more preferably, fully wash with mixed solution or the methyl alcohol of distilled water and distilled water and acetone, room temperature dry or vacuum drying oven dry, obtain final toner.
Preferably, in the time of n=0, described method specifically comprises the steps:
1) room temperature (5-30 DEG C), under protection of inert gas, is dissolved in described aromatic dicarboxylic phenol in organic solvent;
2) in above-mentioned reaction solution, add catalyzer and optional dewatering agent, and be warming up to 50-130 DEG C;
3) after described phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, be slowly added drop-wise in above-mentioned solution;
4) after dropwising, by above-mentioned reaction solution system insulation reaction 5-12 hour;
5) react complete, reaction system is cooled to room temperature, solution system is deposited in several times distilled water or acidic aqueous solution, filtration obtains product, fully wash with mixed solution or the methyl alcohol of distilled water and distilled water and acetone, room temperature dry or vacuum drying oven dry, obtain final toner.
The synthetic route of reaction formula 2:n=0 phthalonitrile monomer
In the time of n=1-4
1) room temperature (5-30 DEG C), under protection of inert gas, is dissolved in described aromatic dicarboxylic phenol and aromatic dicarboxylic halogenated compound in organic solvent;
2) in above-mentioned reaction solution, add after catalyzer and dewatering agent, be warming up to 100-180 DEG C of reflux dewatering reaction 5-15 hour;
3) above-mentioned reaction solution system is controlled to 50-130 DEG C, after described phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, is slowly added drop-wise in above-mentioned solution;
4) after dropwising, by above-mentioned reaction solution system insulation reaction 5-12 hour;
5) react complete, reaction system is cooled to room temperature, solution system is deposited in several times distilled water or acidic aqueous solution, filtration obtains product, fully wash with mixed solution or the methyl alcohol of distilled water and distilled water and acetone, room temperature dry or vacuum drying oven dry, obtain final toner.
The synthetic route of reaction formula 3:n=1-4 phthalonitrile monomer
O-phthalonitrile resin matrix of the present invention is with aromatic dicarboxylic phenol, aromatic dicarboxylic halogenated compound and phthalonitrile base end-capping reagent are raw material, adopt two step method, first dihydric phenol and binary halogenated compound under protection of inert gas, under the effect of catalyzer and dewatering agent, reaction generates bisphenol cpd, then add nitrophthalonitrile compound, at 50-130 DEG C, reaction 5-12 hour, obtain product solution, finally by this solution precipitation in several times distilled water or the olefin(e) acid aqueous solution, through washing, dry, purifying, finally obtain phthalonitrile pressed powder.The 3-nitrophthalonitrile using has increased the asymmetry of molecule, has increased the randomness of resin composition simultaneously, thereby has reduced melting point resin, has improved the solubleness of resin, has reached and has improved the technological object of resin treatment.
The present invention also provides o-phthalonitrile resin mixture of the present invention in the application of preparing in matrix material.
According to the present invention, described o-phthalonitrile resin can freely solidify or mold pressing obtains resin mold casting die, also can be dissolved in organic solvent and the compound prepreg of making of reinforcement, prepare polymer matrix composites by mold pressing or autoclave technique, can also directly prepare matrix material by resin transfer molding (RTM) technique or resin molding infiltration technique (RFI).
Novel ortho phthalonitrile resin of the present invention has lower fusing point, along with backbone structure difference, the difference of capping group proportioning, and the difference of the polymerization degree, resin system melting range, between 25-150 DEG C, is starkly lower than the resin system of traditional single 4-nitrophthalonitrile end-blocking.Than traditional o-phthalonitrile resin (only having 4-nitrophthalonitrile is end-capping reagent), in this resin, introduce the collaborative end-blocking of 3-nitrophthalonitrile, thereby increased the asymmetry of resin structure, increase the randomness (seeing formula 1) of resin Composition.And this resin system has good solubleness in the intensive polar solvent such as DMF, N,N-dimethylacetamide, solubleness is apparently higher than the resin system of traditional single 4-nitrophthalonitrile end-blocking.In addition, rheometer test demonstration, Novel ortho phthalonitrile resin of the present invention, than the o-phthalonitrile resin of 4-nitro end-blocking, has lower melt viscosity, wider process window, is applicable to the composite material process planning method such as mould pressing process, resin transfer molding (RTM).This resin system can solidify at 150-170 DEG C, carries out aftertreatment and solidify between 250-375 DEG C.
Reaction of the present invention is the nucleophilic substitution reaction under base catalysis, and the ratio feeding intake by control and speed can obtain having the different o-phthalonitrile resins that form structures and different proportion of composing, after precipitation washing purifying, obtains rosthomite powder.
Novel ortho phthalonitrile resin of the present invention is than traditional o-phthalonitrile resin, there is melt temperature low, solvability is good, the features such as process window is wide, and solidification value is low, the resin mold casting die of preparation and matrix material porosity prepared by resin matrix is low, fine heat-resisting performance, mechanical property is higher, can be used as lightweight, high-temperature-resistant structure parts in aerospace, space technology, the high-technology field application such as machinofacture.And owing to having lower water-intake rate, excellent fire-retardant fireproof performance, can apply in marine ship field.
Embodiment
The present invention is described in detail by following embodiment.But it will be appreciated by those skilled in the art that following embodiment is not limiting the scope of the invention.Any improvement of making on basis of the present invention and variation, all within protection domain of the present invention.
Embodiment 1
Under room temperature nitrogen protection, by 0.2mol4,4'-'-biphenyl diphenol is dissolved in 2.34mol DMF (DMF), and adds wherein 0.3mol Anhydrous potassium carbonate, is warming up to 80 DEG C.0.15mol4-nitrophthalonitrile and 0.25mol3-nitrophthalonitrile are dissolved in 4.68mol DMF, slowly drop in above-mentioned solution, after dropwising, remain on 80 DEG C of reactions 8 hours.After completion of the reaction, first solution system is down to room temperature, then solution is slowly deposited in 5 times of distilled water, obtain brown color precipitation, be precipitated to filtrate clarification and pH value is neutral with distilled water repetitive scrubbing, in 60 DEG C of vacuum drying ovens dry 8 hours, obtain brown color powdered product, product structure is shown below, productive rate 85%.
This resin softening point 85-90 DEG C, melt temperature is reacted than 4-nitrophthalonitrile and 4,4'-'-biphenyl diphenol the product (fusing point 232-237 DEG C) obtaining and is reduced and exceed 100 DEG C.
Under nitrogen protection, o-phthalonitrile resin obtained above is heated to molten state, adds wherein 5%-10% mol ratio containing amino catalyzer, evenly after blend, be cooled to room temperature.Above-mentioned resin dissolves, at DMF solution, and is carried out to the compound prepreg of preparing with high-strength glass cloth, after most of solvent that volatilizees, will preimpregnation cloth place in 120 DEG C of convection oven dry 2 hours.Take out preimpregnation cloth and superpose as requested in laying placement mould, mould is put into press, 140 DEG C of insulations are after 0.5 hour, directly be warming up to 170 DEG C, the 1-1.5 1.0MPa that as a child pressurizeed, 170 DEG C of insulations 3 hours, then 200 DEG C of insulation 1h, then be warming up to 250 DEG C of insulation 5h.Naturally cold going to room temperature, obtains phthalonitrile composite material laminated board, puts into the free aftertreatment of baking oven 315 DEG C/3 hours+375 DEG C/5 hours.The second-order transition temperature of veneer sheet is greater than 450 DEG C (DMA), and 5% weightless temperature is greater than 520 DEG C (TGA).
Embodiment 2
Under room temperature nitrogen protection; by 0.2mol dihydroxyphenyl propane and 0.1mol4; 4 '-difluoro benzophenone is dissolved in 7.2mol N-Methyl pyrrolidone (NMP); and add wherein 0.4mol Anhydrous potassium carbonate, be warming up to 100 DEG C, stirring reaction 1 hour; then in water trap, fill it up with toluene; in reaction system, add 20ml toluene, be warming up to 170-175 DEG C of back flow reaction 14 hours, except the water of dereaction generation.Reaction soln is cooled to 60 DEG C, 0.05mol4-nitrophthalonitrile and 0.05mol3-nitrophthalonitrile are dissolved in 2.34mol NMP, slowly drop in above-mentioned solution, after dropwising, remain on 60 DEG C of reactions 6 hours.After completion of the reaction, first solution system is down to room temperature, then solution is slowly deposited in 5 times of dilute hydrochloric acid distilled water solutions, obtain brown precipitate, be precipitated to filtrate clarification and pH value is neutral with distilled water repetitive scrubbing, more further wash crude product with the mixed solvent of acetone and water, wash complete, room temperature is dried, obtain final product, structure is shown below, softening temperature 50-55 DEG C, decline and exceeded 50 DEG C, productive rate 78% than only reacting with 4-nitrophthalonitrile the product obtaining.
Embodiment 3
Under room temperature argon shield; 0.3mol Resorcinol and 0.2mol isophthalic dibromo are dissolved in to 10.8mol N; in dinethylformamide (DMF); and add wherein 0.0064mol1; 10-phenanthrolene, 0.0035mol cuprous iodide and 0.7mol Anhydrous potassium carbonate are then filled it up with toluene in water trap, in reaction system, add 20ml toluene; be warming up to 140-145 DEG C of back flow reaction 16 hours, no longer include water and generate.Reaction soln is cooled to 80 DEG C, 0.025mol4-nitrophthalonitrile and 0.075mol3-nitrophthalonitrile are dissolved in 2.34mol DMF, slowly drop in above-mentioned solution, after dropwising, remain on 80 DEG C of reactions 8 hours.After completion of the reaction, first solution system is down to room temperature, then solution is slowly deposited in 6 times of dilute hydrochloric acid frozen water solution, obtain brown precipitate, be precipitated to filtrate clarification and pH value is neutral with frozen water repetitive scrubbing, further wash crude product with methyl alcohol again, wash completely, room temperature is dried 48 hours, obtain brown color product, room temperature is semi-solid state, and softening temperature declines approximately 10 DEG C than 4-nitrophthalonitrile end-blocking product, productive rate 86%.
Under nitrogen protection, o-phthalonitrile resin obtained above is heated to molten state, adds wherein 5%-10% mol ratio containing amino catalyzer, evenly after blend, be cooled to room temperature.Above-mentioned resin dissolves, at acetone soln, and is carried out to the compound prepreg of preparing with high-strength glass cloth, after most of solvent that volatilizees, will preimpregnation cloth place in 50 DEG C of convection oven dry 2 hours.Take out preimpregnation cloth and superpose as requested in laying placement mould, mould is put into press, 140 DEG C of insulations are after 0.5 hour, directly be warming up to 170 DEG C, the 1-1.5 1.0MPa that as a child pressurizeed, 170 DEG C of insulations 3 hours, then 200 DEG C of insulation 1h, then be warming up to 250 DEG C of insulation 5h.Naturally cold going to room temperature, obtains phthalonitrile composite material laminated board, puts into the free aftertreatment of baking oven 315 DEG C/3 hours+375 DEG C/5 hours.The second-order transition temperature of veneer sheet is greater than 350 DEG C (DMA), and 5% weightless temperature is greater than 500 DEG C (TGA).
Embodiment 4
Under room temperature nitrogen protection, 0.2mol Resorcinol is dissolved in 3.51mol DMF (DMF), and adds wherein 0.3mol Anhydrous potassium carbonate, be warming up to 80 DEG C.0.2mol4-nitrophthalonitrile and 0.2mol3-nitrophthalonitrile are dissolved in 4.68mol DMF, slowly drop in above-mentioned solution, after dropwising, remain on 80 DEG C of reactions 8 hours.After completion of the reaction, first solution system is down to room temperature, then solution is slowly deposited in 5 times of distilled water, obtain brown color precipitation, be precipitated to filtrate clarification and pH value is neutral with distilled water repetitive scrubbing, in 60 DEG C of vacuum drying ovens dry 8 hours, obtain brown color powdered product, product structure is shown below, productive rate 88%.This resin softening point 70-75 DEG C, the product (185 DEG C of fusing points) that melt temperature obtains than 4-nitrophthalonitrile and resorcin reaction reduces and exceedes 100 DEG C.
Under nitrogen protection, o-phthalonitrile resin obtained above is heated to molten state, adds wherein 5%-10% mol ratio containing amino catalyzer, evenly after blend, be cooled to room temperature.Above-mentioned resin dissolves, at acetone soln, and is carried out to the compound prepreg of preparing with high-strength glass cloth, after most of solvent that volatilizees, will preimpregnation cloth place in 50 DEG C of convection oven dry 2 hours.Take out preimpregnation cloth and superpose as requested in laying placement mould, mould is put into press, 140 DEG C of insulations are after 0.5 hour, directly be warming up to 170 DEG C, the 1-1.5 1.0MPa that as a child pressurizeed, 170 DEG C of insulations 3 hours, then 200 DEG C of insulation 1h, then be warming up to 250 DEG C of insulation 5h.Naturally cold going to room temperature, obtains phthalonitrile composite material laminated board, puts into the free aftertreatment of baking oven 315 DEG C/3 hours+375 DEG C/5 hours.The second-order transition temperature of veneer sheet is greater than 450 DEG C (DMA), and 5% weightless temperature is greater than 515 DEG C (TGA).
Embodiment 5
Under room temperature nitrogen protection; 0.2mol Resorcinol and 0.1mol bis-(4-fluorophenyl) phenyl phosphine oxide are dissolved in to 8.4mol N; in N-N,N-DIMETHYLACETAMIDE; and add wherein 0.4mol Anhydrous potassium carbonate, be warming up to 110 DEG C, stirring reaction 1 hour; then in water trap, fill it up with toluene; in reaction system, add 20ml toluene, be warming up to 150-155 DEG C of back flow reaction 12 hours, except the water of dereaction generation.Reaction soln is cooled to 60 DEG C, 0.05mol4-nitrophthalonitrile and 0.05mol3-nitrophthalonitrile are dissolved in 2.68mol DMAc, slowly drop in above-mentioned solution, after dropwising, remain on 60 DEG C of reactions 8 hours.After completion of the reaction, first solution system is down to room temperature, then solution is slowly deposited in 5 times of dilute hydrochloric acid distilled water solutions, obtain brown precipitate, be precipitated to filtrate clarification and pH value is neutral with distilled water repetitive scrubbing, more further wash crude product with the mixed solvent of acetone and water, wash complete, room temperature is dried
Obtain final product, structure is shown below, and softening temperature 40-45 DEG C has declined and exceedes 30 DEG C, productive rate 76% than only reacting with 4-nitrophthalonitrile the product obtaining.
Experimental example
The molar ratio of the mixture in embodiment 1-5 can be by controlling rate of addition, reaction times and controlling.Particularly, in the mixture obtaining by the preparation method of embodiment of the present invention 1-5, the mol ratio of formula (1), formula (2) and formula (3) is (20-45): (40-60): (10-25), and preferably (25-40): (45-55): (12-20), be more preferably 36:49:15.
Table 3,4 has been listed respectively thermal characteristics and the mechanical property of virgin resin cured article and the different forming method T300 carbon fibre reinforced composites of embodiment of the present invention 1-3.
Table 3 typical o-phthalonitrile resin cured article thermal characteristics and mechanical property
| Second-order transition temperature/DEG C | 350-475 | Adopt DMA method to measure |
| Shock strength/KJ/m 2 | 5-20 | GB/T2571-1995 |
| Flexural strength/MPa | 82-118 | GB/T2570-1995 |
| Modulus in flexure/GPa | 3.8-4.6 | GB/T2570-1995 |
The typical T300 carbon fiber of table 4 strengthens o-phthalonitrile resin composite materials property
(compression molding & RTM moulding)
Note: bending property detection standard: GB/T3356-1999; Interlayer shear Performance Detection standard: GB/T3357-82.
Claims (10)
1. an o-phthalonitrile resin, is characterized in that, described resin is selected from the mixture as shown in the formula three kinds of polymkeric substance shown in (1), formula (2) or formula (3),
Wherein, n
1, n
2, n
3be selected from independently of one another the integer of 0-4;
R in various
1be selected from independently of one another
R
2be selected from independently of one another
R
3be selected from independently of one another
2. according to the resin of claim 1, it is characterized in that, in described mixture, the mol ratio of formula (1), formula (2) and formula (3) is (20-45): (40-60): (10-25), preferably (25-40): (45-55): (12-20), be more preferably 36:49:15.
3. according to the resin of claim 1 or 2, it is characterized in that R in described formula (1)
1with R in formula (2) and formula (3)
1for same structure; Or R in formula (1)
2with R in formula (2) and formula (3)
2for same structure; Or, R in formula (1)
3with R in formula (2) and formula (3)
3for same structure.
4. a preparation method for the o-phthalonitrile resin of claim 1-3 any one, is characterized in that, described step comprises:
After described phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, slowly be added drop-wise in the solution of the aromatic dicarboxylic phenol that is dissolved in organic solvent and optional aromatic dicarboxylic halogenated compound, under the condition of catalyzer and optional dewatering agent, o-phthalonitrile resin is prepared in reaction.
Wherein, R1, R2, R3, n1, n2, the definition of n3 is as defined above.
5. according to the preparation method of claim 4, it is characterized in that,
Work as n1, n2, when n3=0, after phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, slowly be added drop-wise in the aromatic dicarboxylic phenol solution being dissolved in organic solvent the mixture of reaction preparation o-phthalonitrile resin of the present invention under the condition of catalyzer and optional dewatering agent.Or,
Work as n1, n2, when the integer of n3=1-4, after described phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, slowly be added drop-wise in the aromatic dicarboxylic phenol and aromatic dicarboxylic halogenated compound solution being dissolved in organic solvent, under the condition of catalyzer and optional dewatering agent, o-phthalonitrile resin is prepared in reaction.
Preferably, described phthalonitrile-terminated dose is selected from 3-nitro-1,2-phthalonitrile or 3-nitro-1,2-phthalonitrile and 4-nitro-1, the mixture of 2-phthalonitrile.
Preferably, described aromatic dicarboxylic phenol is pyrocatechol, Resorcinol, and Resorcinol, 4,4'-'-biphenyl diphenol, 4,4'-dioxydiphenyl methane, dihydroxyphenyl propane, 6F dihydroxyphenyl propane, containing a kind of in polyimide structures dihydric phenol or the mixture of any two kinds wherein.
Preferably, described aromatic dicarboxylic halogenated compound is 4,4 '-difluoro benzophenone, isophthalic dibromo, two (4-fluorophenyl) phenyl phosphine oxide, a kind of in 4,4'-dichloro diphenyl sulfone or the wherein mixture of any two kinds.
6. according to the preparation method of claim 4 or 5, it is characterized in that, the molfraction ratio of described aromatic dicarboxylic phenol, aromatic dicarboxylic halogenated compound and O-phthalic itrile group end-capping reagent is: (n+1): n:2, and wherein n=0-4, n comprises n1, n2, n3 any one.
Preferably, described organic solvent is DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone, or it mixes arbitrarily.
Described catalyzer is that Anhydrous potassium carbonate, anhydrous sodium carbonate, potassium hydroxide, sodium hydroxide or its mix arbitrarily.
State the mixture that dewatering agent is cuprous iodide and phenanthrolene.
7. according to the preparation method of claim 4-6 any one, it is characterized in that, described aromatic dicarboxylic phenol and optional aromatic dicarboxylic halogenated compound at room temperature, are dissolved in organic solvent under protection of inert gas.
Preferably; described method comprises: at described aromatic dicarboxylic phenol and optional aromatic dicarboxylic halogenated compound under room temperature (as 5-30 DEG C); after be dissolved in organic solvent under protection of inert gas in, add catalyzer and optional dewatering agent, and be warming up to 50-130 DEG C.
Preferably, described method be also included in above-mentioned reaction complete after, make reaction system insulation reaction 5-12 hour, preferably 6-10 hour.
Also more preferably, after insulation reaction, reaction system is cooled to room temperature, solution system is deposited in several times distilled water or acidic aqueous solution, filter and obtain product.Also more preferably, fully wash with mixed solution or the methyl alcohol of distilled water and distilled water and acetone, room temperature dry or vacuum drying oven dry, obtain final toner.
8. according to the preparation method of claim 4-7 any one, it is characterized in that, in the time of n=0, described method specifically comprises the steps:
1) room temperature (5-30 DEG C), under protection of inert gas, is dissolved in described aromatic dicarboxylic phenol in organic solvent;
2) in above-mentioned reaction solution, add catalyzer and optional dewatering agent, and be warming up to 50-130 DEG C;
3) after described phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, be slowly added drop-wise in above-mentioned solution;
4) after dropwising, by above-mentioned reaction solution system insulation reaction 5-12 hour;
5) react complete, reaction system is cooled to room temperature, solution system is deposited in several times distilled water or acidic aqueous solution, filtration obtains product, fully wash with mixed solution or the methyl alcohol of distilled water and distilled water and acetone, room temperature dry or vacuum drying oven dry, obtain final toner.
In the time of n=1-4
1) room temperature (5-30 DEG C), under protection of inert gas, is dissolved in described aromatic dicarboxylic phenol and aromatic dicarboxylic halogenated compound in organic solvent,
2) in above-mentioned reaction solution, add after catalyzer and dewatering agent, be warming up to 100-180 DEG C of reflux dewatering reaction 5-15 hour;
3) above-mentioned reaction solution system is controlled to 50-130 DEG C, after described phthalonitrile-terminated dose is dissolved in organic solvent according to a certain ratio, is slowly added drop-wise in above-mentioned solution;
4) after dropwising, by above-mentioned reaction solution system insulation reaction 5-12 hour;
5) react complete, reaction system is cooled to room temperature, solution system is deposited in several times distilled water or acidic aqueous solution, filtration obtains product, fully wash with mixed solution or the methyl alcohol of distilled water and distilled water and acetone, room temperature dry or vacuum drying oven dry, obtain final toner.
9. the o-phthalonitrile resin mixture of claim 1-3 any one is in the application of preparing in resin mold casting die or polymer matrix composites.
10. the o-phthalonitrile resin mixture of claim 1-3 any one or the resin mold casting die of claim 9 or polymer matrix composites are in aerospace, space technology, the application in machinofacture.
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