CN105331104A - Modified thermosetting resin and preparation method thereof - Google Patents
Modified thermosetting resin and preparation method thereof Download PDFInfo
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- CN105331104A CN105331104A CN201510914051.XA CN201510914051A CN105331104A CN 105331104 A CN105331104 A CN 105331104A CN 201510914051 A CN201510914051 A CN 201510914051A CN 105331104 A CN105331104 A CN 105331104A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention discloses modified thermosetting resin and a preparation method thereof. 100 parts of molten state thermosetting resin and 1-20 parts of fluorine-containing-polyimide-b-polysiloxane rigid-flexible segmented copolymer with amino end groups are evenly mixed and undergo a curing and postprocessing process to obtain fluorine-containing-polyimide-b-polysiloxane rigid-flexible segmented copolymer modified thermosetting resin. The modified thermosetting resin has high heat resistance, high toughness, low dielectric constant and good curing manufacturability. The method for preparing the modified thermosetting resin is simple and practical, no solvent is used, and the modified thermosetting resin undergoes large-scale and cleaning production easily.
Description
Technical field
The present invention relates to modified heat convertible resin and preparation method thereof, particularly a kind of fluorinated polyimide-polysiloxane block copolymers modified heat convertible resin and preparation method thereof.
Background technology
The develop rapidly in the sophisticated industry fields such as electronic information, insulation electrical, new forms of energy, aerospace, to their Common key base mateiral----thermosetting resin proposes more higher performance requriementss, wherein mainly comprises high heat resistance, excellent in toughness, low-k and excellent curing process etc.
In order to meet the requirement of high-performance thermosetting resin, generally based on heat-resisting thermosetting resin, carry out study on the modification." fragility " is the intrinsic outstanding problem of thermosetting resin.How to realize toughness reinforcing on the basis of not sacrificing original thermosetting resin premium properties, be the important content of thermosetting resin research and development always, be also one and be rich in challenging work.
In recent years, the research of block copolymer-toughened epoxy thermoset is utilized to attract attention.Compared with Traditional project thermoplastic polymer hot in nature, in segmented copolymer, the existence of opposed polarity segment can make segmented copolymer and resin compatible, and the poor compatibility occurred when solving engineered thermoplastic polymer toughening is difficult to the problem of disperseing in thermosetting resin.Simultaneously, the intersegmental chemical structure of chain of segmented copolymer and polarity difference make it in resin, form nanostructure, the Nano microsphere formed is by the cavitation effect of soft core, change three axial stresses around hole into two dimension thus cause a large amount of shear zone and toughness reinforcing, Nano microsphere and interfacial detachment also sponge part stress.Therefore, the toughening mechanism of segmented copolymer includes interface debonding, cavitation, the mechanism and multiple such as crack deflection.But, the correlative study in this direction focus mostly on epoxy resin toughness reinforcing in.Be worth pointing out, the segmented copolymer adopted mostly is amphipathic nature block polymer, and substantially containing the hydrophilic segment such as polycaprolactone, polyoxyethylene, not only thermotolerance is lower for they, and easily moisture absorption, is not suitable for the modification of thermotolerance thermosetting resin.
On the other hand, the segmented copolymer of existing amphipathic nature block polymer is all based on flexible chain, thermotolerance and rigidity relative deficiency.So far, the blended work of rigidity_flexibility combination (being made up of rigidity and soft segment) and heat-resisting thermosetting resin can be reported (see document: WDeng see the research of the people such as Deng, YZhong, JQin, XHuangandJPeng.Morphologycontrolofporousepoxyresinbyrod-coilblockoligomer:aself-assembly-inducedphaseseparationb ydiphenylfluorene-modifiedsiliconeepoxy [J] .RSCAdvances, 2014,4 (57): 30028-30034).The pattern controlling porous epoxy resin is separated by rigidity_flexibility combination oligopolymer self-assembly induction phase, illustrate that rigidity_flexibility combination can self-assembly in resin, but the research done, does not relate to the impact of this segmented copolymer on the physical and chemical performance of epoxy resin.Further, owing to becoming porous resin with the blended obtained epoxy resin of rigidity_flexibility combination, greatly limit the range of application of resin.Also can learn from the report of document, the self-assembled structures of this segmented copolymer is spherical micelle.And find in the research of existing amphipathic nature block polymer modified resin, the toughening effect of vermiculate glues is better than spherical micelle.Research as people such as Liu is reported (see document: JLiu, ZJThompson, HJSue, FSBates, MAHillmyer, MDettloff, GJacob, NVergheseandHPham.Tougheningofepoxieswithblockcopolymerm icellesofwormlikemorphology [J] .Macromolecules, 2010,43 (17): 7238-7243), when self-assembled structures is spherical micelle, toughness reinforcing amplitude is 84%, and the toughness reinforcing amplitude of vermicular texture is 106%.Therefore, the rigidity_flexibility combination that research and development have vermicular texture can obtain higher toughness, is also conducive to the thermotolerance keeping even improving heat-resisting thermosetting resin.
As previously mentioned, low-k is the important performance indexes of the field such as electronic information, insulation electrical performance resins, but in the research to block copolymer-modified thermosetting resin, prior art not yet relates to its dielectric properties.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, provide one to have technological heat resistance thermosetting resin of high tenacity, low-k and good solidification and preparation method thereof.
Realize the preparation method that technical scheme that the object of the invention adopts is to provide a kind of modified heat convertible resin, by mass, the thermal curable resin of 100 parts of molten states is mixed with 1 ~ 20 part of segmented copolymer be made up of fluorinated polyimide and polysiloxane segment, after solidification, aftertreatment technology, namely obtain a kind of modified heat convertible resin.
Thermal curable resin of the present invention is at least containing bismaleimides, a kind of in cyanate ester resin or their combination.The number-average molecular weight of the segmented copolymer of described fluorinated polyimide and polysiloxane segment composition is 5000 ~ 20000.In mass ratio, fluorinated polyimide and polysiloxane segment are 9: 1 ~ 7: 3.
The preparation method of the segmented copolymer of fluorinated polyimide of the present invention and polysiloxane segment composition comprises the steps: by mass,
1, be 20 ~ 30 DEG C in temperature, under protection of inert gas condition, 10 parts of diamines be dissolved in 168 ~ 337 parts of N, in N '-dimethyl ethanamide, obtain solution A;
2, under agitation, join in solution A by 24 parts of hexafluorodianhydrides, after adding, temperature rises to 150 ~ 155 DEG C, and insulation reaction 1 ~ 3h, obtains solution B;
3, be, under the condition of 20 ~ 30 DEG C, 4.3 ~ 12.8 parts of Amino End Group polydimethylsiloxanes are dissolved in 30 ~ 89 parts of N, in N '-dimethyl ethanamide, obtain solution C in temperature;
4, be, under the condition of 150 ~ 155 DEG C, solution C is dropwise joined in solution B in temperature; After dropwising, add 30 ~ 60 parts of toluene; Be warming up to 180 ~ 185 DEG C, insulation reaction 4 ~ 8h; After reaction terminates, obtain reaction system D;
5, the temperature of reaction system D is down to 20 ~ 30 DEG C, slowly joins in the methyl alcohol of 840 ~ 1685 parts, stir and obtain powdery precipitate, then through super-dry, obtain crude product E;
6, crude product E is after purification, drying treatment, namely obtains the segmented copolymer of a kind of fluorinated polyimide and polysiloxane segment composition.
Described diamines is 4, the one in 4 '-diaminodiphenyl oxide, DDS, or their arbitrary combination.Described rare gas element is nitrogen, argon gas have in one.In above-mentioned steps 2, hexafluorodianhydride is divided into three batches and adds, 5 ~ 10min of being at every turn separated by.
Technical solution of the present invention also comprises a kind of modified heat convertible resin obtained by above-mentioned preparation method.
Compared with prior art, the beneficial effect acquired by the present invention is:
1, a kind of rigidity_flexibility combination to be made up of polyimide (rigidity) and polysiloxane (flexibility) segment of design and synthesis of the present invention (is denoted as fluorinated polyimide in the present invention
-b-polysiloxane), it spontaneously forms a kind of vermiculate glues structure with thin solvent borne core and solvation shell of nano-scale in thermosetting resin, has high toughening effect.Meanwhile, this segmented copolymer (fluorinated polyimide
-b-polysiloxane) with bismaleimides and cyanate ester resin, there is good consistency, the former can be made to be dispersed in resin, to give full play to toughening effect.
2, the modified heat convertible resin that obtains of the present invention is while acquisition excellent toughness, also has outstanding thermotolerance, rigidity and dielectric properties.This comes from polyimide rigid chain segment to have fragrant heterocycle structure, ensure that thermostability and the rigidity of resin, and fluorine-containing rigid chain segment and the polysiloxane segment with low-k ensure that resin has lower specific inductivity.
3, the segmented copolymer (fluorinated polyimide of the present invention's employing
-b-polysiloxane) with heat-resisting thermosetting resin, there is good consistency, by scorification preparation, and do not use solvent, therefore, prepare the simple for process of modified heat convertible resin, condition of molding is not harsh.
4, rigidity_flexibility combination disclosed in this invention (is designated as fluorinated polyimide
-b-polysiloxane) structure by regulating the ratio of soft, hard section with the obtained segmented copolymer with different structure, to prepare the adjustable modified heat convertible resin of Structure and Properties, the requirement in different application field can be met, having the advantages that suitability is wide.
Accompanying drawing explanation
Fig. 1 is the fluorinated polyimide that the embodiment of the present invention 1 provides
-b-the building-up reactions schematic flow sheet of polysiloxane block copolymers;
Fig. 2 is the fluorinated polyimide that the embodiment of the present invention 1 provides
-b-the proton nmr spectra of polysiloxane block copolymers (
1h-NMR) figure;
Fig. 3 is the fluorinated polyimide that the embodiment of the present invention 1 provides
-b-infrared (FTIR) spectrogram of polysiloxane block copolymers;
Fig. 4 is the fluorinated polyimide that the embodiment of the present invention 1 ~ 3 provides
-b-thermal weight loss (TG) curve of polysiloxane block copolymers and difference quotient thermogravimetic analysis (TGA) (DTG) curve comparison figure;
Fig. 5 is scanning differential calorimetric (DSC) the curve comparison figure of the performed polymer of the thermosetting resin that the embodiment of the present invention 1,2 and 3 and comparative example 1 provide;
Fig. 6 is the thermogravimetric curve figure of the cyanate ester resin that the modified cyanic acid ester resin that provides of the embodiment of the present invention 1 ~ 6 and comparative example 1 provide.
Fig. 7 is the shock strength comparison diagram of the cyanate ester resin that the modified cyanic acid ester resin that provides of the embodiment of the present invention 1 ~ 6 and comparative example 1 provide.
Fig. 8 is the Fracture Toughness comparison figure of the cyanate ester resin that the modified cyanic acid ester resin that provides of the embodiment of the present invention 1 ~ 6 and comparative example 1 provide.
Fig. 9 is the flexural strength comparison diagram of the cyanate ester resin that the modified cyanic acid ester resin that provides of the embodiment of the present invention 1 ~ 6 and comparative example 1 provide.
Figure 10 is the specific inductivity-frequency curve comparison diagram of the cyanate ester resin that the modified cyanic acid ester resin that provides of the embodiment of the present invention 1 ~ 6 and comparative example 1 provide.
Figure 11 is the atomic force microscope figure of the modified cyanic acid ester resin that the embodiment of the present invention 2 provides.
Figure 12 is the atomic force microscope figure of the modified cyanic acid ester resin that the embodiment of the present invention 3 provides.
Embodiment
Below in conjunction with accompanying drawing, embodiment and comparative example, technical solution of the present invention will be further described.
Embodiment 1
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers multipolymer
N
2under protection, at 25 DEG C, by 0.6726g4,4 '-diaminodiphenyl oxide is dissolved in 15mLN, and N '-dimethyl ethanamide, obtains solution A; 1.5927g hexafluorodianhydride is added solution A, and then temperature rises to 150 DEG C, and insulation reaction 2h, obtain solution B; At 25 DEG C, by 0.2870g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 2mLN, N '-dimethyl ethanamide, obtains solution C; At 150 DEG C, in solution B, dropwise add solution C, then add 3mL toluene; Be warming up to 180 DEG C, reaction 4h, obtains reaction system D; The temperature of reaction system D is down to 25 DEG C, is slowly poured in 100mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E.Crude product E is dissolved in 10mL methylene dichloride, then uses 80mL methanol extraction.Dry 5h at 120 DEG C, at 80 DEG C after dry 10h, obtains fluorinated polyimide
-b-polysiloxane block copolymers.The number-average molecular weight of this fluorinated polyimide-b-polysiloxane block copolymers is 10105g/mol, and the ratio of fluorinated polyimide and polysiloxane segment is 9:1.Fluorinated polyimide
-b-the building-up reactions formula of polysiloxane block copolymers, proton nmr spectra, infrared spectrum and thermogravimetric curve are shown in accompanying drawing 1,2,3 and 4 respectively.
(2) preparation of modified cyanic acid ester resin cured article
Polyimide prepared by 3.5g step (1)
-b-polysiloxane block copolymers and two (the 4-cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 70g2,2'-add in beaker, and at 160 DEG C, mechanical stirring is to polyimide
-b-polysiloxane block copolymers dissolves completely, obtains dark-brown clear liquid; At 160 DEG C, pre-polymerization 2h, obtains performed polymer, and its DSC curve is see accompanying drawing 5.
Obtained performed polymer is poured in preheated mould, at 160 DEG C, vacuumize 1h; Then be cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtain a kind of fluorinated polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.Its thermogravimetric curve, shock strength, fracture toughness property, flexural strength, specific inductivity-frequency curve are shown in accompanying drawing 6,7,8,9 and 10 respectively.
See accompanying drawing 1, it is the fluorinated polyimide that the present embodiment provides
-b-the synthesis flow schematic diagram (reaction formula) of polysiloxane block copolymers, this reaction relates to condensation polymerization reaction, and the segmented copolymer obtained is two ends is amino segmented copolymer.
See accompanying drawing 2, it is the fluorinated polyimide that the present embodiment provides
-b-the proton nmr spectra of polysiloxane block copolymers.Displacement is the signal of hydrogen atom on polyimide phenyl ring at 5 groups of peaks at δ=8.05 ~ 7.19 place, and displacement and the strength of signal ratio at each group peak are substantially identical; The peak at δ=3.76 ~ 3.60 place corresponds to-CH
2the proton of the upper methylene radical of-N-, the vibration peak at δ=1.74 ~ 1.62 place corresponds to-CH
2the proton of-upper methylene radical, the vibration peak at δ=0.5 ~ 0.6 place corresponds to-CH
2the proton of the upper methylene radical of-Si-, the peak at δ=0 ~ 0.2 place corresponds to-Si-CH
3the proton of upper methyl.Consistent with calculated value by the integral area at nuclear-magnetism peak, thus can determine that this product is polyimide-b-polysiloxane block copolymers multipolymer really.
See accompanying drawing 3, it is the fluorinated polyimide that the present embodiment provides
-b-the infrared spectrum of polysiloxane block copolymers.This spectrogram there is in succession the charateristic avsorption band (2960cm representing methyl in polysiloxane
-1), the unsymmetrically of C-O and symmetrical stretching vibration absorption peak (1783cm in polyimide structures
-1, 1728cm
-1), on phenyl ring the stretching vibration of C=C absorb (1623cm
-1), the charateristic avsorption band (1502cm of C-F
-1), the stretching vibration absorption peak (1376cm of C-N
-1), the stretching vibration absorption peak (1148cm of Si-O-Si
-1, 1094cm
-1) and Si-C key absorption peak (801cm
-1), illustrate and successfully synthesize target product.
Embodiment 2
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers
N
2under protection, at 25 DEG C, by 0.5381g4,4 '-diaminodiphenyl oxide is dissolved in 13mLN, and N '-dimethyl ethanamide, obtains solution A; 1.3439g hexafluorodianhydride is added solution A; Then temperature rises to 150 DEG C, and insulation reaction 2h, obtain solution B; At 25 DEG C, by 0.4305g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 3mLN, N '-dimethyl ethanamide, obtains solution C.At 150 DEG C, in solution B, dropwise add solution C, then add 2.5mL toluene, be warming up to 180 DEG C, reaction 4h, obtains reaction system D; Reaction system D temperature is down to 25 DEG C, is slowly poured in 80mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E, be dissolved in 8mL methylene dichloride, again use 65mL methanol extraction.Dry 5h at 120 DEG C, obtains fluorinated polyimide-polysiloxane block copolymers multipolymer at 80 DEG C after dry 10h.The number-average molecular weight of this fluorinated polyimide-b-polysiloxane block copolymers is 7805g/mol, and the ratio of fluorinated polyimide and polysiloxane segment is 8:2.Fluorinated polyimide
-b-thermal weight loss and difference quotient thermal weight loss (DTG) curve of polysiloxane block copolymers are shown in accompanying drawing 4.
(2) preparation of modified cyanic acid ester resin cured article
Take the fluorinated polyimide that 3.5g step (1) provides
-b-propane is in beaker for polysiloxane block copolymers and 70g2,2'-two (4-cyanogen oxygen phenyl), and at 160 DEG C, mechanical stirring is dissolved completely to segmented copolymer, obtain dark-brown clear liquid, at 160 DEG C, pre-polymerization 2h, obtains performed polymer, and its DSC curve is shown in accompanying drawing 5.
The performed polymer obtained being poured in preheated mould, at 160 DEG C, vacuumize 1h, being cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtaining a kind of fluorinated polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.Its thermogravimetric curve, shock strength, fracture toughness property, flexural strength, specific inductivity-frequency curve and atomic force microscope figure are shown in accompanying drawing 6,7,8,9,10 and 11 respectively.
Embodiment 3
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers
N
2under protection, at 25 DEG C, by 0.4484g4,4 '-diaminodiphenyl oxide is dissolved in 10mLN, and N '-dimethyl ethanamide, obtains solution A; 1.1945g hexafluorodianhydride is added solution A; After adding, temperature rises to 150 DEG C, and insulation reaction 2h obtains solution B; At 25 DEG C, by 0.5740g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 4mLN, N '-dimethyl ethanamide, obtains solution C.At 150 DEG C, in solution B, dropwise add solution C, then add 2mL toluene, be warming up to 180 DEG C, reaction 4h, obtains reaction system D; Reaction system D temperature is down to 25 DEG C, is slowly poured in 70mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E, be dissolved in 7mL methylene dichloride, again use 50mL methanol extraction.Dry 5h at 120 DEG C, obtains fluorinated polyimide-polysiloxane block copolymers multipolymer at 80 DEG C after dry 10h.The number-average molecular weight of this fluorinated polyimide-b-polysiloxane block copolymers is 5486g/mol, and the ratio of fluorinated polyimide and polysiloxane segment is 7:3.Fluorinated polyimide
-b-the thermogravimetric curve of polysiloxane block copolymers is shown in accompanying drawing 4.
(2) preparation of modified cyanic acid ester resin cured article
Take the fluorinated polyimide that 3.5g step (1) provides
-b-propane is in beaker for polysiloxane block copolymers and 70g2,2'-two (4-cyanogen oxygen phenyl), and at 160 DEG C, mechanical stirring is dissolved completely to segmented copolymer, obtain dark-brown clear liquid, at 160 DEG C, pre-polymerization 2h, obtains performed polymer, and its DSC curve is shown in accompanying drawing 5.
The performed polymer obtained being poured in preheated mould, at 160 DEG C, vacuumize 1h, being cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtaining a kind of fluorinated polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.Its thermogravimetric curve, shock strength, fracture toughness property, flexural strength, specific inductivity-frequency curve and atomic force microscope figure are shown in accompanying drawing 6,7,8,9,10 and 12 respectively.
See accompanying drawing 4, it is the fluorinated polyimide that the embodiment of the present invention 1 ~ 3 is synthesized
-b-thermal weight loss (TG) curve of polysiloxane block copolymers and difference quotient thermal weight loss (DTG) analytic curve, as seen from the figure, the fluorinated polyimide that embodiment 1,2 and 3 is synthesized
-b-initial decomposition temperature (temperature during initial weightless 5wt%, the T of polysiloxane block copolymers
di) be 482 DEG C respectively, 469 DEG C and 461 DEG C.Known in conjunction with DTG curve, the decomposition of segmented copolymer is carried out in two steps, from about 400 DEG C decompose, to when 520 DEG C for reaching maximum heat rate of decomposition corresponding temperature (T
max); Next 540 DEG C time, the decomposition of subordinate phase is started, to decomposing rate when 560 DEG C to maximum.Illustrate that the segmented copolymer of synthesis has excellent thermotolerance.
The preparation of comparative example 1: take 70g2, two (the 4-cyanogen oxygen phenyl) propane of 2'-is in beaker, and at 160 DEG C, mechanical stirring is to melting, and obtains light yellow clear liquid.At 160 DEG C after pre-polymerization 2h, obtain performed polymer, its DSC curve is shown in accompanying drawing 5.Performed polymer is poured in preheated mould, with 160 DEG C at vacuumize 1h, then to be cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, to obtain cyanate thermosets, be designated as cyanate.Its thermogravimetric curve, shock strength, fracture toughness property, flexural strength and specific inductivity are shown in accompanying drawing 6,7,8,9 and 10 respectively.
See accompanying drawing 5, it is the DSC curve of the performed polymer of the thermosetting resin that the embodiment of the present invention 1 ~ 3 and comparative example 1 provide.Therefrom can find out, add fluorinated polyimide
-b-after polysiloxane block copolymers, the whole curing reaction peak of modified resin appears at low temperature direction, this is because there is active Amino End Group at segmented copolymer two ends, can catalysis cyanate ester monomer polymerization and with cyanate ester monomer copolymerization.This advantage overcomes the shortcoming of the high reaction temperature that heat stable resin usually exists.
Embodiment 4
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers multipolymer
N
2under protection, at 25 DEG C, by 0.6726g4,4 '-diaminodiphenyl oxide is dissolved in 15mLN, and N '-dimethyl ethanamide, obtains solution A; 1.5927g hexafluorodianhydride is added solution A, and then temperature rises to 150 DEG C, and insulation reaction 2h, obtain solution B; At 25 DEG C, by 0.2870g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 2mLN, N '-dimethyl ethanamide, obtains solution C; At 150 DEG C, in solution B, dropwise add solution C, then add 3mL toluene; Be warming up to 180 DEG C, reaction 4h, obtains reaction system D; The temperature of reaction system D is down to 25 DEG C, is slowly poured in 100mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E.Crude product E is dissolved in 10mL methylene dichloride, then uses 80mL methanol extraction.Dry 5h at 120 DEG C, at 80 DEG C after dry 10h, obtains fluorinated polyimide
-b-polysiloxane block copolymers.The number-average molecular weight of this fluorinated polyimide-b-polysiloxane block copolymers is 10105g/mol, and the ratio of fluorinated polyimide and polysiloxane segment is 9:1.
(2) preparation of modified cyanic acid ester resin cured article
Take the fluorinated polyimide that 7g step (1) provides
-b-propane is in beaker for polysiloxane block copolymers and 70g2,2'-two (4-cyanogen oxygen phenyl), and at 160 DEG C, mechanical stirring is dissolved completely to segmented copolymer, obtains dark-brown clear liquid, at 160 DEG C after pre-polymerization 2h, obtains performed polymer.
The performed polymer obtained being poured in preheated mould, at 160 DEG C, vacuumize 1h, being cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtaining a kind of fluorinated polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.Its thermogravimetric curve, shock strength, fracture toughness property, flexural strength and specific inductivity-frequency curve are shown in accompanying drawing 6,7,8,9 and 10 respectively.
Embodiment 5
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers
N
2under protection, at 25 DEG C, by 0.5381g4,4 '-diaminodiphenyl oxide is dissolved in 13mLN, and N '-dimethyl ethanamide, obtains solution A; 1.3439g hexafluorodianhydride is added solution A; Then temperature rises to 150 DEG C, and insulation reaction 2h, obtain solution B; At 25 DEG C, by 0.4305g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 3mLN, N '-dimethyl ethanamide, obtains solution C.At 150 DEG C, in solution B, dropwise add solution C, then add 2.5mL toluene, be warming up to 180 DEG C, reaction 4h, obtains reaction system D; Reaction system D temperature is down to 25 DEG C, is slowly poured in 80mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E, be dissolved in 8mL methylene dichloride, again use 65mL methanol extraction.Dry 5h at 120 DEG C, obtains fluorinated polyimide-polysiloxane block copolymers multipolymer at 80 DEG C after dry 10h.The number-average molecular weight of this fluorinated polyimide-b-polysiloxane block copolymers is 7805g/mol, and the ratio of fluorinated polyimide and polysiloxane segment is 8:2.
(2) preparation of modified cyanic acid ester resin cured article
Take the fluorinated polyimide that 7g step (1) provides
-b-propane is in beaker for polysiloxane block copolymers and 70g2,2'-two (4-cyanogen oxygen phenyl), and at 160 DEG C, mechanical stirring is dissolved completely to segmented copolymer, obtains dark-brown clear liquid, at 160 DEG C after pre-polymerization 2h, obtains performed polymer.
The performed polymer obtained being poured in preheated mould, at 160 DEG C, vacuumize 1h, being cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtaining a kind of polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.Its thermogravimetric curve, shock strength, fracture toughness property, flexural strength and specific inductivity are shown in accompanying drawing 6,7,8,9 and 10 respectively.
Embodiment 6
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers
N
2under protection, at 25 DEG C, by 0.4484g4,4 '-diaminodiphenyl oxide is dissolved in 10mLN, and N '-dimethyl ethanamide, obtains solution A; 1.1945g hexafluorodianhydride is added solution A; After adding, temperature rises to 150 DEG C, and insulation reaction 2h obtains solution B; At 25 DEG C, by 0.5740g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 4mLN, N '-dimethyl ethanamide, obtains solution C.At 150 DEG C, in solution B, dropwise add solution C, then add 2mL toluene, be warming up to 180 DEG C, reaction 4h, obtains reaction system D; Reaction system D temperature is down to 25 DEG C, is slowly poured in 70mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E, be dissolved in 7mL methylene dichloride, again use 50mL methanol extraction.Dry 5h at 120 DEG C, obtains fluorinated polyimide-polysiloxane block copolymers multipolymer at 80 DEG C after dry 10h.The number-average molecular weight of this fluorinated polyimide-b-polysiloxane block copolymers is 5486g/mol, and the ratio of fluorinated polyimide and polysiloxane segment is 7:3.
(2) preparation of modified cyanic acid ester resin cured article
Take the polyimide that 7g step (1) provides
-b-propane is in beaker for polysiloxane block copolymers and 70g2,2'-two (4-cyanogen oxygen phenyl), and at 160 DEG C, mechanical stirring is dissolved completely to segmented copolymer, obtains dark-brown clear liquid, after 160 DEG C of pre-polymerization 2h, obtains performed polymer.
The performed polymer obtained being poured in preheated mould, at 160 DEG C, vacuumize 1h, being cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtaining a kind of polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.Its thermogravimetric curve, shock strength, fracture toughness property, flexural strength and specific inductivity are shown in accompanying drawing 6,7,8,9 and 10 respectively.
See accompanying drawing 6, it is fluorinated polyimide prepared by the embodiment of the present invention 1 ~ 6
-b-the thermogravimetric curve of cyanate ester resin prepared by polysiloxane block copolymers modified cyanic acid ester resin and comparative example 1.Can find out, these resins have substantially identical curve, and T
diabout the same, illustrate and adopt polyimide
-b-polysiloxane block copolymers modification does not have the original superior heat-stability of deteriorated cyanate ester resin.
See accompanying drawing 7, it is fluorinated polyimide prepared by the embodiment of the present invention 1 ~ 6
-b-the shock strength figure of cyanate ester resin prepared by polysiloxane block copolymers modified cyanic acid ester resin and comparative example 1.Can find out, the shock strength of the cyanate ester resin that the shock strength of the modified cyanic acid ester resin that embodiment 1 ~ 6 provides all provides far above comparative example 1, increase rate is between 140% ~ 253%, and this increase rate is significantly higher than the increase rate reported in document.As, the PEO-PPO-PEO segmented copolymer of 5wt% is added into separately cyanate-epoxy resins by the people such as Hu, its notched impact strength rises 20%, when addition is increased to 10wt%, notched impact strength rises 30%(and sees: CHu, JYu, JHuo, YChen, HFMa.EffectofclayandPEO-PPO-PEOblockcopolymeronthemicros tructureandpropertiesofcyanateester/epoxycomposite [J] .CompositesPartA:AppliedScienceandManufacturing, 2015, 78:113-123.), fluorinated polyimide prepared by the present invention is described
-b-polysiloxane block copolymers has significant toughened ability.
Above-mentioned conclusion, further can be confirmed by comparing fracture toughness property.See accompanying drawing 8, it is fluorinated polyimide prepared by the embodiment of the present invention 1 ~ 6
-b-the fracture toughness property figure of cyanate ester resin prepared by polysiloxane block copolymers modified cyanic acid ester resin and comparative example 1.The Fracture Toughness of modified resin is all higher than the value of the cyanate ester resin of comparative example 1 preparation.From embodiment 1 ~ 3, the addition of segmented copolymer is 5wt%, and content of soft segmer rises gradually; From embodiment 4 ~ 6, the addition of segmented copolymer is 10wt%, and content of soft segmer rises gradually.Visible, along with fluorinated polyimide
-b-content of soft segmer in polysiloxane block copolymers rises, and the fracture toughness property of system rises thereupon.And in modified resin prepared by embodiment 3, segmented copolymer is with vermiculate glues distribution in matrix, the fracture toughness property of modified resin reaches maximum value, is 3.9 times of cyanate ester resin value prepared by comparative example 1.In modified resin prepared by embodiment 6, the flexible chain content of segmented copolymer is the highest, and the fracture toughness property of modified resin reaches 3.7 times of cyanate ester resin value.The people such as Wu are by sulfonated polystyrene
-b-poly-(ethene
-co-butylene)
-b-vinylbenzene adds epoxy resin, when the addition of segmented copolymer is respectively 5wt% and 10wt%, the fracture toughness property of modified resin is successively for 1.7 and 1.8 times of epoxy resin value are (see SWu, QGuo, MKraska, BStuhn, YWMai.Tougheningepoxythermosetswithblockionomers:therole ofphasedomainsize [J] .Macromolecules, 2013,46 (20): 8190-8202.).By documents, can find out, segmented copolymer provided by the invention has excellent toughening effect.
See accompanying drawing 9, it is fluorinated polyimide prepared by the embodiment of the present invention 1 ~ 6
-b-the flexural strength figure of cyanate ester resin prepared by polysiloxane block copolymers modified cyanic acid ester resin and comparative example 1.General bending intensity is commonly used to the comprehensive mechanical property of exosyndrome material, is the result of rigidity and toughness comprehensive action.Accompanying drawing 9 shows, the flexural strength (126MPa) of the cyanate ester resin that the flexural strength of the modified resin that embodiment 1 ~ 6 provides all provides far above comparative example 1, increase rate between 45% ~ 73%, and contrasts pertinent literature, adds the decline that block can cause the bending property of resin.As the PEO-PPO-PEO segmented copolymer of 5% is added into separately cyanate-epoxy resins by the people such as Hu, the flexural strength of matrix material have dropped 2.6%(and sees: CHu, JYu, JHuo, YChen, HFMa.EffectofclayandPEO-PPO-PEOblockcopolymeronthemicros tructureandpropertiesofcyanateester/epoxycomposite [J] .CompositesPartA:AppliedScienceandManufacturing, 2015, 78:113-123.), demonstrate the comprehensive mechanical property that segmented copolymer prepared by the present invention significantly can improve cyanate ester resin, this is the advantage that general plasticized modifier does not have.
See accompanying drawing 10, it is fluorinated polyimide prepared by the embodiment of the present invention 1 ~ 6
-b-specific inductivity-the frequency curve of cyanate ester resin prepared by polysiloxane block copolymers modified cyanic acid ester resin and comparative example 1.Can see, in cyanate ester resin, add fluorinated polyimide
-b-polysiloxane block copolymers effectively can reduce the specific inductivity of resin., this comes from the fluorine atom contained in segmented copolymer to possess lower mole polarizability, and the specific inductivity of polyimide is reduced, and polysiloxane is also low dielectric constant materials simultaneously.
See accompanying drawing 11, it is fluorinated polyimide prepared by the embodiment of the present invention 2
-b-the atomic force microscope figure of polysiloxane block copolymers modified cyanic acid ester resin.Polyimide can be seen
-b-polysiloxane block copolymers defines vermiculate glues in resin matrix.
See accompanying drawing 12, it is fluorinated polyimide prepared by the embodiment of the present invention 3
-b-the atomic force microscope figure of polysiloxane block copolymers modified cyanic acid ester resin.Can see, fluorinated polyimide
-b-polysiloxane block copolymers defines vermiculate glues in resin matrix.
Above-mentioned data show, compare original cyanate ester resin (comparative example 1), fluorinated polyimide disclosed by the invention
-b-polysiloxane block copolymers modified heat convertible resin, on the basis of thermostability keeping excellence, not only has lower solidification value and specific inductivity, the toughness significantly improved and comprehensive mechanical property, proves fluorinated polyimide disclosed by the invention
-b-polysiloxane block copolymers is a kind of multifunctional modification agent.
Embodiment 7
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers multipolymer
Under argon shield, at 20 DEG C, by 0.6726g4,4 '-diaminodiphenyl oxide is dissolved in 11.3mLN, and N '-dimethyl ethanamide, obtains solution A; 1.5927g hexafluorodianhydride is added solution A, and then temperature rises to 155 DEG C, and insulation reaction 1h, obtain solution B; At 20 DEG C, by 0.2870g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 2mLN, N '-dimethyl ethanamide, obtains solution C; At 155 DEG C, in solution B, dropwise add solution C, then add 2mL toluene; Be warming up to 183
oc, reaction 8h, obtains reaction system D; The temperature of reaction system D is down to 20 DEG C, is slowly poured in 56.5mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E.Crude product E is dissolved in 6.7mL methylene dichloride, then uses 33.6mL methanol extraction.Dry 5h at 120 DEG C, at 80 DEG C after dry 10h, obtains fluorinated polyimide
-b-polysiloxane block copolymers.The number-average molecular weight of this fluorinated polyimide-b-polysiloxane block copolymers is 11033g/mol, and the ratio of fluorinated polyimide and polysiloxane segment is 9:1.
(2) preparation of modified cyanic acid ester resin cured article
Polyimide prepared by 0.7g step (1)
-b-polysiloxane block copolymers and two (the 4-cyanogen oxygen phenyl) propane (also known as bisphenol A cyanate ester) of 70g2,2'-add in beaker, and at 160 DEG C, mechanical stirring is to polyimide
-b-polysiloxane block copolymers dissolves completely, obtains dark-brown clear liquid.At 160 DEG C, pre-polymerization 2h, obtains performed polymer, is poured into by obtained performed polymer in preheated mould, at 160 DEG C, vacuumizes 1h; Then be cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtain a kind of fluorinated polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.
Embodiment 8
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers
Under argon shield, at 30 DEG C, by 0.5381g4,4 '-diaminodiphenyl oxide is dissolved in 18mLN, and N '-dimethyl ethanamide, obtains solution A; 1.3439g hexafluorodianhydride is added solution A; After adding, temperature rises to 152
oc, insulation reaction 3h, obtain solution B; At 30 DEG C, by 0.4305g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 3mLN, N '-dimethyl ethanamide, obtains solution C.152
ounder C, in solution B, dropwise add solution C, then add 3.2mL toluene, be warming up to 185 DEG C, reaction 6h, obtains reaction system D; Reaction system D temperature is down to 30 DEG C, is slowly poured in 90.7mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E, be dissolved in 10.8mL methylene dichloride, again use 80.7mL methanol extraction.Dry 5h at 120 DEG C, obtains fluorinated polyimide-polysiloxane block copolymers multipolymer at 80 DEG C after dry 10h.The number-average molecular weight of this fluorinated polyimide-b-polysiloxane block copolymers is 6716g/mol, and the ratio of fluorinated polyimide and polysiloxane segment is 8:2.
(2) preparation of modified cyanic acid ester resin cured article
Take the fluorinated polyimide that 14g step (1) provides
-b-polysiloxane block copolymers and 70g2, two (the 4-cyanogen oxygen phenyl) propane of 2'-is in beaker, at 160 DEG C, mechanical stirring is dissolved completely to segmented copolymer, obtain dark-brown clear liquid, at 160 DEG C, pre-polymerization 2h, obtains performed polymer, the performed polymer obtained is poured in preheated mould, at 160 DEG C, vacuumizing 1h, being cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtaining a kind of fluorinated polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.
Embodiment 9
(1) fluorinated polyimide
-b-the preparation of polysiloxane block copolymers
N
2under protection, at 25 DEG C, by 0.5567g4,4 '-diaminodiphenylsulfone(DDS) is dissolved in 11mLN, and N '-dimethyl ethanamide, obtains solution A; 1.1945g hexafluorodianhydride is added solution A; After adding, temperature rises to 155 DEG C, and insulation reaction 3h obtains solution B; At 25 DEG C, by 0.5740g Amino End Group polydimethylsiloxane, (molecular weight is 1280g/mol, and viscosity is 40mm
2/ g) be dissolved in 4mLN, N '-dimethyl ethanamide, obtains solution C.At 155 DEG C, in solution B, dropwise add solution C, then add 2.5mL toluene, be warming up to 180 DEG C, reaction 4h, obtains reaction system D; Reaction system D temperature is down to 25 DEG C, is slowly poured in 60mL methyl alcohol and stirs, being settled out powdery product, through super-dry, obtaining crude product E, be dissolved in 9mL methylene dichloride, again use 60mL methanol extraction.Dry 5h at 120 DEG C, obtains fluorinated polyimide-polysiloxane block copolymers multipolymer at 80 DEG C after dry 10h.
(2) preparation of modified cyanic acid ester resin cured article
Take the fluorinated polyimide that 3.5g step (1) provides
-b-propane is in beaker for polysiloxane block copolymers and 70g2,2'-two (4-cyanogen oxygen phenyl), and at 160 DEG C, mechanical stirring is dissolved completely to segmented copolymer, and obtain dark-brown clear liquid, at 160 DEG C, pre-polymerization 2h, obtains performed polymer.The performed polymer obtained being poured in preheated mould, at 160 DEG C, vacuumize 1h, being cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, obtaining a kind of fluorinated polyimide
-b-polysiloxane block copolymers modified cyanic acid ester resin, is designated as PI
-b-pDMS/ cyanate.
Embodiment 10
The present embodiment provides a kind of preparation method of modified cyanic acid ester-epoxy resin: fluorinated polyimide 2.88g embodiment 1 step (1) provided
-b-polysiloxane block copolymers, 50.01g bisphenol A cyanate ester and 7.61g epoxy resin (trade mark E-51) are mixed to join in beaker, stir 25min, obtain performed polymer at 100 DEG C; Performed polymer is poured in mould, vacuum defoamation 30min, is cured and thermal treatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique, namely obtains modified cyanic acid ester-epoxy resin.
Embodiment 11
The present embodiment provides the preparation method of a kind of modified bismaleimide-cyanate cured resin: under agitation, at 135 DEG C by 8.91g4,4 '-dimaleoyl imino ditane (BDM) and 2 of 6.59g, 2 '-diallyl bisphenol (DBA) mixing also pre-polymerization 35min, obtains BDM/DBA prepolymer.The fluorinated polyimide that 2.88g embodiment 1 step (1) provides is added in BDM/DBA prepolymer
-b-polysiloxane block copolymers and two (the 4-cyanogen oxygen phenyl) propane of 42.01g2,2'-, stir 30min, obtain performed polymer at 150 DEG C; Performed polymer is poured in mould, vacuum defoamation 30min, is cured and thermal treatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/3h technique, namely obtains modified bismaleimide-cyanate ester resin.
Embodiment 12
The present embodiment provides a kind of preparation method of modified bismaleimide resin: take 20g4,4 '-dimaleoyl imino ditane (BDM) and 14.8g2,2 '-diallyl bisphenol (DBA) is in beaker, mechanical stirring pre-polymerization 10min at 135 DEG C, obtains the transparent clarified liq of brown color.Add the fluorinated polyimide that 1.74g embodiment 1 step (1) provides in a liquid
-b-polysiloxane block copolymers, mechanical stirring pre-polymerization 15min, obtains the prepolymer of clear.Prepolymer is poured in preheated mould, vacuumize 1h in 135 DEG C, then be cured and aftertreatment according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h and 240 DEG C/4h technique respectively, obtain a kind of fluorinated polyimide
-b-polysiloxane block copolymers modified bismaleimide resin.
Claims (9)
1. the preparation method of a modified heat convertible resin, it is characterized in that: by mass, the thermal curable resin of 100 parts of molten states is mixed with 1 ~ 20 part of segmented copolymer be made up of fluorinated polyimide and polysiloxane segment, after solidification, aftertreatment technology, namely obtain a kind of modified heat convertible resin.
2. the preparation method of a kind of modified heat convertible resin according to claim 1, is characterized in that: described thermal curable resin is at least containing bismaleimides, a kind of in cyanate ester resin or their combination.
3. the preparation method of a kind of modified heat convertible resin according to claim 1, is characterized in that: the number-average molecular weight of the segmented copolymer of described fluorinated polyimide and polysiloxane segment composition is 5000 ~ 20000.
4. the preparation method of a kind of modified heat convertible resin according to claim 1, is characterized in that: in mass ratio, and fluorinated polyimide and polysiloxane segment are 9: 1 ~ 7: 3.
5. the preparation method of a kind of modified heat convertible resin according to claim 1, is characterized in that: the preparation method of the segmented copolymer of described fluorinated polyimide and polysiloxane segment composition comprises the steps: by mass,
(1) be 20 ~ 30 DEG C in temperature, under protection of inert gas condition, 10 parts of diamines be dissolved in 168 ~ 337 parts of N, in N '-dimethyl ethanamide, obtain solution A;
(2) under agitation, join in solution A by 24 parts of hexafluorodianhydrides, after adding, temperature rises to 150 ~ 155 DEG C, and insulation reaction 1 ~ 3h, obtains solution B;
(3) be, under the condition of 20 ~ 30 DEG C, 4.3 ~ 12.8 parts of Amino End Group polydimethylsiloxanes are dissolved in 30 ~ 89 parts of N, in N '-dimethyl ethanamide, obtain solution C in temperature;
(4) be, under the condition of 150 ~ 155 DEG C, solution C is dropwise joined in solution B in temperature; After dropwising, add 30 ~ 60 parts of toluene; Be warming up to 180 ~ 185 DEG C, insulation reaction 4 ~ 8h; After reaction terminates, obtain reaction system D;
(5) temperature of reaction system D is down to 20 ~ 30 DEG C, slowly joins in the methyl alcohol of 840 ~ 1685 parts, stir and obtain powdery precipitate, then through super-dry, obtain crude product E;
(6) crude product E is after purification, drying treatment, namely obtains the segmented copolymer of a kind of fluorinated polyimide and polysiloxane segment composition.
6. the preparation method of a kind of modified heat convertible resin according to claim 5, is characterized in that: in step (2), and hexafluorodianhydride is divided into three batches and adds, 5 ~ 10min of being at every turn separated by.
7. the preparation method of a kind of modified heat convertible resin according to claim 5, is characterized in that: described diamines is 4, the one in 4 '-diaminodiphenyl oxide, DDS, or their arbitrary combination.
8. the preparation method of a kind of modified heat convertible resin according to claim 5, is characterized in that: described rare gas element is nitrogen, argon gas have in one.
9. by a kind of modified heat convertible resin that preparation method according to claim 1 obtains.
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