CN101037528A - Heat-resistant bismaleimide/epoxy resin and preparation method thereof - Google Patents
Heat-resistant bismaleimide/epoxy resin and preparation method thereof Download PDFInfo
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- CN101037528A CN101037528A CN 200710040055 CN200710040055A CN101037528A CN 101037528 A CN101037528 A CN 101037528A CN 200710040055 CN200710040055 CN 200710040055 CN 200710040055 A CN200710040055 A CN 200710040055A CN 101037528 A CN101037528 A CN 101037528A
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- bismaleimide
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Abstract
The invention discloses a heat-resistant bimaleimide/epoxy resin and preparing method thereof, which includes steps: (1) adding chain expansion agent to bimaleimide, under temperature of 130-180 DEG C, reacting for 15-150 min, adding solvent and obtaining bimaleimide prepolymer; (2) mixing the bimaleimide prepolymer prepared by step (1) and epoxy resin under temperature of 120-180 DEG C, and obtaining bimaleimide/epoxy resin; (3) curing the bimaleimide/epoxy resin prepared by step (2) under temperature of 130-280 DEG C for 2-8 h, and obtaining the heat-resistant bimaleimide/epoxy resin. Advantages of the prepared bimaleimide/epoxy resin are: cohesive strength and heat endurance of the resin is enhanced, residual curing stress is reduced due to prolonged molecular chain, operation is simple, cost is low, and industrial production is convenient.
Description
Technical field
The present invention relates to adopt the bismaleimides of chain extension and the method that Resins, epoxy prepares a kind of heat-resistant bismaleimide/epoxy resin.
Background technology
Bismaleimides is a kind of intermediate of addition polyimide, and the molecule two ends are active end group with the unsaturated maleimide ring, and structure can be expressed as:
Wherein: R is CH
2, SO
2, O;
Bimaleimide resin has good high temperature resistant, moisture-resistance, also have advantages such as starting material wide material sources, cost are lower simultaneously, since 1969 were succeeded in developing by French Rhone Poulenc company, countries such as the U.S., Britain, Germany, Japan, China researched and developed in succession.As the matrix resin bimaleimide resin of a class ideal advanced composite material in department's widespread uses such as space flight and aviation, mechano-electronic, communications and transportation.But general general bimaleimide resin cross-linking density is too high, so fragility is big.
U.S. Pat, 3920768 (1975) disclose a kind of diamine modified bismaleimide, though use diamine modified bismaleimide system to have good thermotolerance, mechanical property and toughness, manufacturability is relatively poor, the prepreg of making does not almost have viscosity.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of Resins, epoxy that contains the bismaleimide amine component and preparation method thereof, to overcome the deficiencies in the prior art.
Span/epoxy heat stable resin that the present invention proposes, the preparation method comprises the steps:
(1) bismaleimides chain extending reaction:
Chainextender is added bismaleimides, and 130 ℃～180 ℃, reaction 15min～150min adds solvent then, and bismaleimides performed polymer that can be behind chain extension, this performed polymer then play the solidifying agent effect mixing with Resins, epoxy.
Said bismaleimides is selected from one or more in diphenyl methane dimaleimide, phenyl ether bismaleimides or the sulfobenzide bismaleimides;
Said chainextender is N, N '-two amido sulfobenzide, N, N '-two amido diphenyl sulfide or N, one or more in the N '-two amido ditane;
Said solvent is N, more than one in N '-dimethyl formamide or the N-pyrrolidone etc.;
Bismaleimides: chainextender=1～4: 1, mol ratio.
In the solvent, the concentration of bismaleimides is 0.001mol/ml～0.1mol/ml;
(2) preparation of bismaleimide/epoxy resin:
The chain extension bismaleimides of step (1) is descended and epoxy blends at 120～180 ℃, promptly obtain bismaleimide/epoxy resin;
Bismaleimides: Resins, epoxy=1～20: 15～5, mass ratio;
The preferred oxirane value of said Resins, epoxy is 0.51 F-51 type Resins, epoxy;
(3) curing of bismaleimide/epoxy resin:
The bismaleimide/epoxy resin of step (2) is solidified 2h～8h under 130 ℃～280 ℃, can obtain the bismaleimide/epoxy resin cured article of heat resistant type;
The preferred following steps that adopt are carried out segmentation curing:
The prepared bismaleimide/epoxy resin of step (2) is carried out segmentation solidifies, 150 ℃ 2 hours, 180 ℃ 2 hours, 220 ℃ 2 hours, 240 ℃ 1 hour, can obtain the product of completion of cure at last;
Bismaleimide/epoxy resin cured article to step (3) gained carries out the thermal weight loss test, can find out from TG figure, and in the time of 400 ℃, weightless 5%, 700 ℃ of weightlessness is complete.Compared to general epoxy resin cured product or with the thermal characteristics of the epoxy resin cured product of other method of modifying modifications, the resistance toheat of the bismaleimide/epoxy resin cured article that the present invention obtains is significantly improved.And moulding process is simple, is a kind of superior matrix materials such as heat-resisting, shock resistance, electrical isolation that have.This resin can be widely used in the dipping of special transformer embedding, various electric motor, engine, high pressure choke coil, satisfies the heat-resisting requirement of superpower, high-voltage, electrical part.
Method of the present invention, with full contraposition N, N '-two amido benzene sulfone and bismaleimides are optimal selection by Micheal addition reaction chain extension, so both can improve the polarity of solidifying agent, the easy and further crosslinking reaction of epoxy of the performed polymer of generation, improve cohesive strength, the resistance toheat of resin, because of the prolongation of molecular chain, reduced residual solidified stress again, made simple to operate, cost is lower, is convenient to suitability for industrialized production.
Description of drawings
Fig. 1 is the thermogravimetric curve of the bismaleimide/epoxy resin of embodiment 1.
Embodiment
Below by embodiment the present invention is carried out concrete description.Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified that can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Diphenyl methane dimaleimide industrial goods among the embodiment 1, impurity :≤0.1%, fusing point: 152-160 ℃, produced by Honghu, Hubei Province bismaleimide resin factory, two amido sulfobenzides are chemical pure, purity 〉=98.0%, fusing point 189.0-191.0, Chemical Reagent Co., Ltd., Sinopharm Group produces; Phenyl ether bismaleimides among the embodiment 2 is that the laboratory is synthetic, synthetic method reference: D.O.Humme, K.U.Heinen, H.Stenzenberger, and H.Siesler.Appl.Polym.Sci.18,2015 (1974); Two amido ditanes are chemical pure, purity 〉=98.0%, and fusing point 120.0-121.0, Chemical Reagent Co., Ltd., Sinopharm Group produces; Phenol aldehyde type epoxy resin F-51 is industrial goods, oxirane value 0.51, and N, N '-dimethyl formamide are analytical pure, purity 〉=99.0%, reagent one factory in Shanghai produces.
Embodiment 1
The preparation of the bismaleimide amine hardener of (1) two amido sulfobenzide chain extension:
The diphenyl methane dimaleimide of 0.15mol mole and the chainextender two amido sulfobenzides (mol ratio is 3: 1) of 0.05mol mole are joined in the reactor that has agitator, thermometer and logical condensing works, be heated with stirring to the system fusion, 170 ℃ ± 10 ℃ reactions of temperature 1.5 hours, add 2ml solvent N at last, N '-dimethyl formamide obtains the pre-polymerization solidifying agent---the bismaleimide amine hardener of two amido sulfobenzide chain extensions russet;
Contain the preparation of the Resins, epoxy of bismaleimides:
(2) with 5 grams of the pre-polymerization solidifying agent in the step (1), have in the reactor of agitator, thermometer and condensing works with 5 gram F-51 Resins, epoxy addings, under 120 ℃ ± 10 ℃ of temperature, stirring reaction 30 minutes.After the temperature of said mixture reduced to room temperature, can obtain the brown solid bismaleimide/epoxy resin;
(3) bismaleimide/epoxy resin solidifies:
The prepared bismaleimide/epoxy resin of step (2) is carried out segmentation solidifies, 150 ℃ 2 hours, 180 ℃ 2 hours, 220 ℃ 2 hours, 240 ℃ 1 hour, can obtain the product of completion of cure at last.
Bismaleimide/epoxy resin cured article to step (3) gained carries out thermal weight loss test (thermal gravimetric analyzer TGA2050 type, U.S. TA company), sees Fig. 1, can find out from TG figure, and in the time of 400 ℃, weightless 5%, 700 ℃ of weightlessness is complete.
Bismaleimide/epoxy resin cured article to step (3) gained carries out electric performance test (wideband dielectric impedance spectrometer CONCEPT 40 types, Germany NOVOCONTROL company), dielectric coefficient is 3.4 relatively, and dielectric loss angle tangent 0.0043, volume resistivity are 7.960 * 10
16, surface resistivity is 3.055 * 10
5
Embodiment 2
The preparation of the bismaleimide amine hardener of (1) two amido ditane chain extension
With the phenyl ether bismaleimides of 0.02mol and the two amido ditanes of 0.005mol (mol ratio is 4: 1), join in the reactor that has agitator, thermometer and logical condensing works, be heated with stirring to the system fusion, 120 ℃ ± 10 ℃ reactions of temperature 15 minutes, add 20ml solvent N at last, N '-dimethyl formamide obtains the bismaleimide amine hardener of two amido ditane chain extensions russet.
(2) contain the preparation of the Resins, epoxy of bismaleimides
Under heated and stirred, with 5 grams of the pre-polymerization solidifying agent in the step (1) and 7 gram F-51 Resins, epoxy, adding has in the reactor of agitator, thermometer and condensing works, under 160 ℃ ± 10 ℃ of temperature, and stirring reaction 50 minutes.After the temperature of said mixture reduced to room temperature, can obtain the brown solid bismaleimide/epoxy resin.
(3) bismaleimide/epoxy resin solidifies
The prepared bismaleimide/epoxy resin of step (2) is carried out segmentation solidifies, 150 ℃ 3 hours, 190 ℃ 2 hours, 240 ℃ 2 hours, can obtain the product of completion of cure at last.
Bismaleimide/epoxy resin cured article to step (3) gained carries out thermal weight loss test (thermal gravimetric analyzer TGA2050 type, U.S. TA company), sees Fig. 1, can find out from TG figure, and in the time of 400 ℃, weightless 5%, 680 ℃ of weightlessness is complete.
Bismaleimide/epoxy resin cured article to step (3) gained carries out electric performance test (wideband dielectric impedance spectrometer CONCEPT 40 types, Germany NOVOCONTROL company), dielectric coefficient is 3.5 relatively, and dielectric loss angle tangent 0.0038, volume resistivity are 6.876 * 10
16, surface resistivity is 3.035 * 10
5
Claims (8)
1. the preparation method of heat-resistant bismaleimide/epoxy resin comprises the steps:
(1) chainextender is added bismaleimides, 130 ℃～180 ℃, reaction 15min～150min adds solvent then, obtains the bismaleimides performed polymer behind chain extension;
(2) the chain extension bismaleimides with step (1) descends and epoxy blends at 120～180 ℃, promptly obtains bismaleimide/epoxy resin;
(3) curing of bismaleimide/epoxy resin:
The bismaleimide/epoxy resin of step (2) is solidified 2h～8h under 130 ℃～280 ℃, promptly obtain the bismaleimide/epoxy resin cured article of heat resistant type.
2. method according to claim 1 is characterized in that, step (3) adopts following steps to carry out segmentation curing:
The prepared bismaleimide/epoxy resin of step (2) is carried out segmentation solidifies, 150 ℃ 2 hours, 180 ℃ 2 hours, 220 ℃ 2 hours, 240 ℃ 1 hour, can obtain the product of completion of cure at last.
3. method according to claim 1 is characterized in that, said bismaleimides is selected from one or more in diphenyl methane dimaleimide, phenyl ether bismaleimides or the sulfobenzide bismaleimides.
4. method according to claim 1 is characterized in that, said chainextender is N, N '-two amido sulfobenzide, N, N '-two amido diphenyl sulfide or N, one or more in the N '-two amido ditane.
5. method according to claim 1 is characterized in that, said solvent is N, more than one in N '-dimethyl formamide or the N-pyrrolidone.
6. method according to claim 1 is characterized in that bismaleimides: Resins, epoxy=1～20: 15～5, and mass ratio;
Said Resins, epoxy is that oxirane value is 0.51 F-51 type Resins, epoxy;
Bismaleimides: chainextender=1～4: 1, mol ratio.
7. method according to claim 1 is characterized in that, in the solvent, the concentration of bismaleimides is 0.001mol/ml～0.1mol/ml.
8. adopt the heat-resistant bismaleimide/epoxy resin of each described method preparation of claim 1～7.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079875A (en) * | 2010-12-18 | 2011-06-01 | 广东生益科技股份有限公司 | High-heat-resistance halogen-free phosphorus-free thermosetting resin composition, and bonding sheet and copper foil-coated laminated board made of same |
| CN103173086A (en) * | 2011-12-23 | 2013-06-26 | 江苏国力电力安装工程有限公司 | Fire-retardant integrally sprayed polymer anti-corrosion lining material for wet desulphurization chimneys of thermal power plants |
| CN105601924A (en) * | 2016-03-17 | 2016-05-25 | 武汉理工大学 | Modified bismaleimide resin, modified bismaleimide resin/carbon fiber reinforced laminated board and preparation method thereof |
| CN106221130A (en) * | 2016-07-28 | 2016-12-14 | 苏州大学 | A kind of porous polymer material and preparation method thereof |
| CN111965940A (en) * | 2020-08-31 | 2020-11-20 | 浙江福斯特新材料研究院有限公司 | Positive photosensitive polyimide resin composition, method for producing resin composition, and use thereof |
| CN114231230A (en) * | 2021-12-30 | 2022-03-25 | 黑龙江省科学院石油化学研究院 | Adhesive for reducing stress and improving temperature resistance and preparation method thereof |
-
2007
- 2007-04-26 CN CN 200710040055 patent/CN101037528A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079875A (en) * | 2010-12-18 | 2011-06-01 | 广东生益科技股份有限公司 | High-heat-resistance halogen-free phosphorus-free thermosetting resin composition, and bonding sheet and copper foil-coated laminated board made of same |
| CN102079875B (en) * | 2010-12-18 | 2013-01-02 | 广东生益科技股份有限公司 | High-heat-resistance halogen-free phosphorus-free thermosetting resin composition, and bonding sheet and copper foil-coated laminated board made of same |
| CN103173086A (en) * | 2011-12-23 | 2013-06-26 | 江苏国力电力安装工程有限公司 | Fire-retardant integrally sprayed polymer anti-corrosion lining material for wet desulphurization chimneys of thermal power plants |
| CN105601924A (en) * | 2016-03-17 | 2016-05-25 | 武汉理工大学 | Modified bismaleimide resin, modified bismaleimide resin/carbon fiber reinforced laminated board and preparation method thereof |
| CN106221130A (en) * | 2016-07-28 | 2016-12-14 | 苏州大学 | A kind of porous polymer material and preparation method thereof |
| CN111965940A (en) * | 2020-08-31 | 2020-11-20 | 浙江福斯特新材料研究院有限公司 | Positive photosensitive polyimide resin composition, method for producing resin composition, and use thereof |
| CN111965940B (en) * | 2020-08-31 | 2024-03-26 | 杭州福斯特电子材料有限公司 | Positive photosensitive polyimide resin composition, preparation method of resin composition and application of resin composition |
| CN114231230A (en) * | 2021-12-30 | 2022-03-25 | 黑龙江省科学院石油化学研究院 | Adhesive for reducing stress and improving temperature resistance and preparation method thereof |
| CN114231230B (en) * | 2021-12-30 | 2023-10-20 | 黑龙江省科学院石油化学研究院 | Adhesive capable of reducing stress and improving temperature resistance and preparation method thereof |
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Open date: 20070919 |