CN105153683A - Method for preparing toughened resin composition - Google Patents
Method for preparing toughened resin composition Download PDFInfo
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- CN105153683A CN105153683A CN201510447489.1A CN201510447489A CN105153683A CN 105153683 A CN105153683 A CN 105153683A CN 201510447489 A CN201510447489 A CN 201510447489A CN 105153683 A CN105153683 A CN 105153683A
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Abstract
The invention relates to a method for preparing a toughened resin composition. The method comprises the following steps of adding copper phthalocyanine and n-butyl lithium into a methanol solution of potassium hydroxylamine; then, sequentially adding graphene oxide and palmitic acid into the methanol solution, conducting stirring for 4 hours at 60 DEG C, adding ytterbium fluoride into the solution, and conducting an ultrasonic treatment for 2 minutes to obtain a mixture; sequentially adding 1,3,5-triglycidyl-S-triazinetrione and diethyl phosphite into the mixture, and conducting stirring for 8 hours at 110 DEG C; adding a resin prepolymer, polydimethylsiloxane and 2-hexanone into the mixture, and conducting stirring for 3 hours at 115 DEG C; and finally, adding nano-silicon carbide, conducting stirring for one hour at 90 DEG C, and performing volatilization to remove the solvent so as to obtain the toughened resin composition. The toughened resin composition is prepared from simple and easily available raw materials without complicated reactions in the prior art, and has excellent mechanical performance and good curing effect; and a stable structure is formed since the nano-silicon carbide, graphene and other ingredients are synergized to promote the activity of an organic substance chain segment, so that the system embrittlement resistance is further improved, the material toughness is improved, and an unexpected effect is achieved.
Description
Technical field
The invention belongs to advanced composite material technical field, be specifically related to a kind of preparation method of toughened resin composition.
Background technology
The development of the development of material and superconductor, aerospacecraft and guided missile has close ties.Within 1911, start the superconductor of the metal or alloy type developed, at the temperature of liquid helium, just will have supraconductivity.Just supraconductivity is there is under the ceramic mould superconductor starting to develop for 1986 also needs the temperature of liquid nitrogen.Superconductor has special significance to electrotechnology development, but it requires Cryogenic Conditions, and therefore the research of low temperature insulation material is also just risen thereupon.The insulating material used under low temperature should have low-temperature flexibility, to ensure having sufficiently high physical strength and process industrial art performance when low temperature; In electrical insulation capability, dielectric loss angle tangent should low as far as possible (tg δ <10
-5), to reduce dielectric loss heating, save refrigeration expense.For the insulation of superconduction and low temperature winding wire, also should ensure, in the process from room temperature to operating temperature, the cracking that thermal stresses causes not to occur; The cold cycling from room temperature to operating temperature should be able to be tolerated; Superconducting line can not be made to anneal when applying insullac.For flexure reliability, IPC proposes a kind of evaluation method of number of flexings to break, but this test force method due to short time consumption long, sometimes some months is needed, totally unfavorable to research and development product innovation, so Japanese educational circles proposition M1T method carrys out test material single-point bending resistance folding endurance with the folding resistance of evaluating material, the method has test result advantage fast, but very large by the impact of bending head working accuracy, data are unstable.
In conventional low temperature insulation material, solid material has polyethylene, tetrafluoroethylene, voltalef, polyphenylene ethyl and the glass fiber tape with epoxy adhesive; Fluent material directly can adopt the non-conductive liquid of low temperature.Second-order transition temperature is lower, the polymkeric substance that crystallinity is less, and resistance to low temperature is better; Otherwise second-order transition temperature is higher, the polymkeric substance that crystallinity is higher, resistance to low temperature is poorer; Second-order transition temperature is lower and amorphous polymer resistance to low temperature below use temperature is better; From mechanical property, under low temperature, the most serious low-temperature flexibility of toughness of material reduction is main relevant with the lax behavior of low temperature.
The research of nano composite material obtains and develops rapidly, different with nano-phase material from the Nanocrystalline materials that single-phase forms, nano composite material is at least in one direction with the matrix material that nano-grade size is composited by two or more gibbs solid phase.These solid phases can be amorphousness state, miocrystalline state, crystalloid state, and can be inorganic, organically or both have.Cyanate ester resin refers to that molecular structure contains two or above-OCN group, and crosslinking curing forms a class platform thing of stable triazine ring under certain conditions.The network of the triazine ring formed gathers platform thing and has higher thermotolerance, and the cross-linking density of cured article is large.Nano composite material has huge specific surface area, and surface energy is very high, thus has performance more more significant than bulk material, is expected important application in toughening material field.
Summary of the invention
The object of this invention is to provide a kind of preparation method of toughened resin composition, the product obtained has excellent mechanical property.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of preparation method of toughened resin composition, comprises the following steps:
(1) add in ketones solvent by propylene glycol diacrylate, maleic anhydride, back flow reaction 30 minutes, volatilization is except desolventizing; Add m-benzene diisocyanate and toluene again, back flow reaction 70 minutes, revolve and steam except desolventizing obtains resin prepolymer;
(2) CuPc and n-Butyl Lithium are added in the methanol solution of azanol potassium, mix 2 hours; Then add graphene oxide, palmitinic acid successively, stir 4 hours in 60 DEG C, then add and fluoridize ytterbium, supersound process obtains mixture in 2 minutes;
(3) in said mixture, add 1,3,5-three-glycidyl-S-triazinetrione, diethyl phosphite successively, stir 8 hours in 110 DEG C; Add above-mentioned resin prepolymer and polydimethylsiloxane and methyl-n-butyl ketone again, stir 3 hours, finally add nanometer silicon carbide in 115 DEG C, 90 DEG C are stirred 1 hour, and volatilization, except desolventizing, obtains toughened resin composition.
In the present invention, in step (1), the mass ratio of propylene glycol diacrylate, maleic anhydride, m-benzene diisocyanate is 1: 0.3: 0.5; The resinous polymer obtained is bonding, reactive good; Better with all the other component polymerisate lower temperature resistances, mechanical property is strong, good stability.
In the present invention, in step (2), CuPc, n-Butyl Lithium, azanol potassium, graphene oxide, palmitinic acid, the mass ratio fluoridizing ytterbium are (1.5 ~ 2): (2.5 ~ 3.3): (1 ~ 2): (3.5 ~ 4.8): (6 ~ 8): 1; The power of supersound process is 800W.
In the present invention, in step (3), 1,3,5-three-glycidyl-S-triazinetrione, diethyl phosphite, resin prepolymer, polydimethylsiloxane, nanometer silicon carbide and the mass ratio fluoridizing ytterbium are (8 ~ 10): (9 ~ 11): (15 ~ 18): (6 ~ 8): (1 ~ 2): 1.
In the present invention, azanol potassium can form small molecules hapto when resin solidification, is conducive to resin system evenly crosslinked, generally exists with the methanol solution of azanol potassium.Not only be beneficial to the reaction of system, increase the consistency of each component of solid composite material, work in coordination with graphene oxide, diethyl phosphite, under being hit, preventing material failure, increase the mobility of molecular chain, improve the mechanical property of solid material.
In the present invention, organic object is the primary bond composition of toughened resin composition, is also the key ingredient of system high tenacity simultaneously; The performance that state of cure shows for toughened resin composition has material impact, in particular concerns the anti-fragility under force environment after the solidification of toughened resin composition; Solvent can well disperse each reactive component, ensures that each component Contact is good, can add according to response situation.
In the present invention, CuPc, n-Butyl Lithium, fluoridize ytterbium, nanometer silicon carbide is good additive, these additives make each component stable dispersion by space stability ultimate load effect, reach good com-patibilising effect; In the reaction process preparing polymkeric substance, each component can be connected, form good toughness, have the solid phase prod of certain cross-linking density.The invention also discloses toughened resin composition prepared by above-mentioned preparation method.
Insert in mould by toughened resin composition, mold pressing (pressure is 12MPa), namely obtains high-toughness material; Preferably, molding temperature is 75 DEG C; Clamp time is 15 minutes.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention utilizes organo-mineral complexing principle, for the preparation of toughened resin composition each component between consistency good, palmitinic acid has long soft segment, prepare a kind of toughened resin composition thus, there is good mechanical property, adhesiveproperties, resistance toheat, meet the development and application of toughened resin composition.
2. in the present invention, additive particles, micromolecular introducing break the structure of the high rigidity of the symmetry of ring resin cured matter, the tiny crack point of system dispersive stress increases, simultaneously, good dispersion makes to have good interfacial interaction between the additive particles of rigidity and resin group, and stress is mutually transmitted between particle and matrix; Effectively can stop the growth of tiny crack, improve system toughness.
3. disclosed by the inventionly prepare in the raw material of toughened resin composition, raw material is simple and easy to get, and without the need to the complex reaction of prior art, the toughened resin composition of preparation has excellent mechanical property, solidification effect is good, when stressed, the collaborative organism segment that impels of other components such as nanometer silicon carbide and Graphene is movable, unfolds further, form stable structure, thus further increase the anti-fragility of system, improve toughness of material, achieve beyond thought effect.
embodiment:
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Add in butanone by 1Kg propylene glycol diacrylate, 300g maleic anhydride, back flow reaction 30 minutes, volatilization is except desolventizing; Add 500g m-benzene diisocyanate and toluene again, back flow reaction 70 minutes, revolve and steam except desolventizing obtains resin prepolymer;
In the ratio of table 1, CuPc and n-Butyl Lithium are added in the methanol solution of azanol potassium, mix 2 hours; Then add graphene oxide, palmitinic acid successively, stir 4 hours in 60 DEG C, then add and fluoridize ytterbium, supersound process obtains mixture in 2 minutes; In said mixture, add 1,3,5-three-glycidyl-S-triazinetrione, diethyl phosphite successively, stir 8 hours in 110 DEG C; Add above-mentioned resin prepolymer and polydimethylsiloxane and methyl-n-butyl ketone again, stir 3 hours, finally add nanometer silicon carbide in 115 DEG C, 90 DEG C are stirred 1 hour, and volatilization, except desolventizing, obtains toughened resin composition.
Table 1 raw materials quality
Insert in mould by toughened resin composition, mold pressing (pressure is 0.2MPa, temperature is 60 DEG C, time be 180 seconds), namely obtains high-toughness material.
Performance test
The performance test results of above-mentioned high-toughness material is in table 2.
The performance test results of table 2 high-toughness material
Claims (8)
1. a preparation method for toughened resin composition, is characterized in that, comprises the following steps:
(1) add in ketones solvent by propylene glycol diacrylate, maleic anhydride, back flow reaction 30 minutes, volatilization is except desolventizing; Add m-benzene diisocyanate and toluene again, back flow reaction 70 minutes, revolve and steam except desolventizing obtains resin prepolymer;
(2) CuPc and n-Butyl Lithium are added in the methanol solution of azanol potassium, mix 2 hours; Then add graphene oxide, palmitinic acid successively, stir 4 hours in 60 DEG C, then add and fluoridize ytterbium, supersound process obtains mixture in 2 minutes;
(3) in said mixture, add 1,3,5-three-glycidyl-S-triazinetrione, diethyl phosphite successively, stir 8 hours in 110 DEG C; Add above-mentioned resin prepolymer and polydimethylsiloxane and methyl-n-butyl ketone again, stir 3 hours, finally add nanometer silicon carbide in 115 DEG C, 90 DEG C are stirred 1 hour, and volatilization, except desolventizing, obtains toughened resin composition.
2. the preparation method of toughened resin composition according to claim 1, it is characterized in that, in step (1), the mass ratio of propylene glycol diacrylate, maleic anhydride, m-benzene diisocyanate is 1: 0.3: 0.5.
3. the preparation method of toughened resin composition according to claim 1, it is characterized in that, in step (2), CuPc, n-Butyl Lithium, azanol potassium, graphene oxide, palmitinic acid, the mass ratio fluoridizing ytterbium are (1.5 ~ 2): (2.5 ~ 3.3): (1 ~ 2): (3.5 ~ 4.8): (6 ~ 8): 1; The power of supersound process is 800W.
4. the preparation method of toughened resin composition according to claim 1, it is characterized in that, in step (3), 1,3,5-three-glycidyl-S-triazinetrione, diethyl phosphite, resin prepolymer, polydimethylsiloxane, nanometer silicon carbide and the mass ratio fluoridizing ytterbium are (8 ~ 10): (9 ~ 11): (15 ~ 18): (6 ~ 8): (1 ~ 2): 1.
5. according to the toughened resin composition that any one preparation method described in claim 1 ~ 4 obtains.
6. toughened resin composition described in claim 5 is preparing the application in high-toughness material.
7. application according to claim 6, is characterized in that, insert in mould by described toughened resin composition, mold pressing obtains high-toughness material.
8. application according to claim 7, is characterized in that, described molding pressure is 12MPa; Molding temperature is 75 DEG C; Clamp time is 15 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510447489.1A CN105153683A (en) | 2015-07-28 | 2015-07-28 | Method for preparing toughened resin composition |
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| CN201510447489.1A CN105153683A (en) | 2015-07-28 | 2015-07-28 | Method for preparing toughened resin composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017219944A1 (en) * | 2016-06-20 | 2017-12-28 | 山东欧铂新材料有限公司 | Method for preparing graphene-epoxy resin composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357968A (en) * | 2008-09-16 | 2009-02-04 | 中国科学院化学研究所 | Maleic anhydride-grafted polypropylene material and preparation method thereof |
| CN103360569A (en) * | 2012-03-29 | 2013-10-23 | 展辰涂料集团股份有限公司 | Multiple curing resin and preparation method thereof |
| CN103497310A (en) * | 2013-09-26 | 2014-01-08 | 同济大学 | High-strength and high-modulus modified cyanate ester resin composition |
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2015
- 2015-07-28 CN CN201510447489.1A patent/CN105153683A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357968A (en) * | 2008-09-16 | 2009-02-04 | 中国科学院化学研究所 | Maleic anhydride-grafted polypropylene material and preparation method thereof |
| CN103360569A (en) * | 2012-03-29 | 2013-10-23 | 展辰涂料集团股份有限公司 | Multiple curing resin and preparation method thereof |
| CN103497310A (en) * | 2013-09-26 | 2014-01-08 | 同济大学 | High-strength and high-modulus modified cyanate ester resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017219944A1 (en) * | 2016-06-20 | 2017-12-28 | 山东欧铂新材料有限公司 | Method for preparing graphene-epoxy resin composite material |
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Application publication date: 20151216 |