CN103387748A - Organic-inorganic hybrid resin, high-temperature-resistant wave-transmitting composite material and preparation method for the organic-inorganic hybrid resin. - Google Patents
Organic-inorganic hybrid resin, high-temperature-resistant wave-transmitting composite material and preparation method for the organic-inorganic hybrid resin. Download PDFInfo
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Abstract
The invention discloses an organic-inorganic hybrid resin, a high-temperature-resistant wave-transmitting composite material and a preparation method for the organic-inorganic hybrid resin. The hybrid resin has good temperature tolerance. The hybrid resin has decomposition temperatures, in air and nitrogen, both higher than 500 DEG C and the resin residue weight percent after the resin is subjected to atmospheric oxidation at 500 DEG C for 1h is higher than 70%. A quartz-fiber-reinforced composite material prepared from the hybrid resin has advantages comprising good mechanical properties, a bending strength higher than 300 MPa at room temperature and a bending strength reaching 150 MPa at a high temperature of 500 DEG C over quartz-fiber-reinforced composite materials prepared from inorganic resins at present. In addition, the composite material has good dielectric properties at a temperature ranging from room temperature to 500 DEG C and in a 1-12 GHz range, wherein the dielectric constant is less than 3.25 and the dielectric loss is less than 0.012. The composite material can meet high-temperature short-time application requirements for aircrafts comprising missiles, rockets, etc.. The composite material has a good application prospect in the high-temperature-resistant wave-transmitting field.
Description
Technical field
The present invention relates to a kind of organic inorganic hybridization resin and high temperature resistant wave-permeable matrix material and preparation method thereof, belong to the material technology field.
Background technology
Along with the development of aeronautical and space technology, more and more urgent for the demand of the performance resins of resistant to elevated temperatures novel texture, function and structure function one.The aircraft such as rocket, guided missile is in the environment of thermal shocking in flight course, flight velocity is faster, surface temperature is higher, suffered thermal shocking is more serious, such as when aircraft speed, reaching 3 Mach, the aircraft surface temperature reaches 400 ℃, when aircraft speed reaches 4 Mach, its surface temperature is over 600 ℃, thereby require resin material 600 ℃ of high temperature (〉) can keep its member integrity under (in minute) condition when (in second) and low temperature (400-500 ℃) are long in short-term, have certain mechanical strength, and the performance of anti-oxidant, resistant to hydrolysis preferably.In addition, must have again the dielectric properties of excellence as the resin matrix of functional type wave-penetrating composite material, particularly, require its specific inductivity between 1-4, dielectric loss is between 0.0001-0.1, and dielectric constant with temperature changes less than 1%/100 ℃.
Traditional organic resin, comprise that polyimide, span come acid amides, epoxy and cyanaloc oxygenolysis namely to occur in the past at 500 ℃, can not meet service requirements.Silicon-containing polymer, owing to having higher high-temperature stability, weathering resistance and outstanding dielectric properties preferably, is studied much and applies.Russia has developed the silicone resin for the high temperature resistant wave-permeable matrix material, and adds the de-carbon metal oxide in resin, has avoided the decline of high temperature dielectric properties, and its resin grade is MK-9K.But organosilicon polymer is due to the Si-O chain flexibility, and Intermolecular Forces is little, and prepared composite materials property is on the low side.
Patent CN101891957A discloses a kind of method that strengthens organic silicon resin-based high temperature resistant wave-permeable composite materials property.Reinforcing filler improves composite materials property to silsesquioxane POSS by adding the cage shape in the silicone resin matrix as nanometer.But its room temperature flexural strength also only has the 150MPa left and right.
Siliceous poly-aryne resin, due to the existence of alkynyl structure, has improved the degree of crosslinking of resin matrix greatly, thereby resin shows excellent high-temperature stability, and the use temperature scope that is expected at 500 ℃ is applied.China and U.S.A has carried out a large amount of research work in this respect.But the existence of alkynyl is also made troubles to processing, and at first the reaction between alkynyl is very fast, is very easy to cause sudden and violent gathering in solidification process, thereby technology and equipment is required harsh.Secondly, the existence of a large amount of alkynyls also causes high temperature carbon residue rate high, and high temperature dielectric properties descends thereupon.
Summary of the invention
The object of the invention is to overcome the deficiency of existing resin system, a kind of new type resin system is provided, on the high-temperature stability basis that keeps inorganic resin, improve its mechanical property by introducing organic resin, thereby form the organic inorganic hybridization resin that has mechanical property and resistance to elevated temperatures concurrently.
The method for preparing hybrid resin provided by the invention, comprise the steps: to add successively bi-phthalonitrile resin shown in polysilazane resin shown in formula I, formula II and solidifying agent in solvent, carry out blending reaction after mixing, react the complete solvent for use of removing, obtain described hybrid resin;
Formula I
In described formula I, R
1And R
2Identical or different, and all be selected from the aliphatics of C1～C6 and any one in aromatic alkyl;
N is 3～1000;
Formula II
In described formula II, X is any one in following group:
With
Concrete, in described formula I, R
1And R
2All be selected from any one in methyl, ethyl, propyl group, phenyl, allyl group and vinyl;
N is 200;
In aforesaid method, shown in polysilazane resin shown in described formula I and formula II, the mass ratio of bi-phthalonitrile resin is 100:5-100, being specially 100:10-50, is more specifically 100:10,100:20,100:30,100:40,100:50,100:10-40,100:10-30,100:10-20,100:20-50,100:20-40,100:20-30,100:30-50,100:30-40 or 100:40-50;
In described blending reaction step, temperature is room temperature, and the time is 0.5-15 hour, is specially 1-3 hour;
Described solvent is selected from METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide, N, dinethylformamide, N, at least a in N-diethylformamide, N-N-Methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide (DMSO), methylene dichloride, chloroform, tetrahydrofuran (THF) and acetone;
The consumption of described solvent be bi-phthalonitrile resin quality shown in polysilazane resin shown in formula I and formula II and 1-5 doubly, be specially 2-4 doubly, be more specifically 3.6,4.2,4.5,4.6,3.6-4.6,3.6-4.2 or 4.2-4.6 doubly.
Described method also comprises the steps: to add solidifying agent in reaction system before described blending reaction step;
Described solidifying agent is selected from platinum catalyst, naphthenate, carboxylate salt, aminated compounds, peroxide catalyst, azo catalyzer, organo-tin compound and organic titanic compound at least a;
Wherein, described platinum catalyst is specially 1,3-divinyl-1,1,3, and 3-tetramethyl disiloxane platinum (0) (the Speier catalyzer, CAS:68478-92-2) or Karstedt catalyzer (aqueous isopropanol of Platinic chloride);
Described naphthenate and described carboxylate salt are specially naphthenate or the carboxylate salt of lead, zinc, cobalt, iron or the cerium of following element;
Described aminated compounds is specially methylamine, dimethylamine, ethamine, diethylamine, triethylamine, propylamine, dipropyl amine or butylamine;
Described peroxide catalyst is specially dicumyl peroxide (DCP);
Described azo catalyzer is specially Diisopropyl azodicarboxylate (AIBN);
Described organo-tin compound is specially dibutyl tin laurate or stannous octoate;
Described organic titanic compound is specially tetrabutyl titanate;
The add-on of described solidifying agent is the 0.1%-20% of polysilazane resin quality shown in described formula I, is specially 5%.
The present invention also provides a kind of hybrid resin, and this hybrid resin is to obtain according to aforementioned method preparation provided by the invention.
The present invention also provides a kind of method for preparing the hybrid resin cured article.The method comprises the steps: described hybrid resin is warming up to 150 ℃-300 ℃ by room temperature, is incubated after 3-15 hour, is cooled to room temperature, obtains described hybrid resin cured article.
In the described heating step of aforesaid method, temperature rise rate is 1-15 ℃/min, is specially 3 ℃/min; The final temperature of heating step is specially 200 ℃, and soaking time is specially 5 hours;
In described cooling step, rate of temperature fall is 1-15 ℃/min, is specially 5 ℃/min.
The present invention also provides a kind of hybrid resin cured article, and this hybrid resin cured article is prepare according to the method described above and obtain.
The present invention also provides a kind of hybrid resin based composites, and this matrix material is by aforementioned hybrid resin cured article provided by the invention and fibrous;
Or by described hybrid resin cured article, fiber and nanometer inorganic filler, formed.In above-mentioned matrix material, described fiber is quartz textile, specifically is selected from least a in silica fiber cloth and three-dimensional quartz cloth;
Described nanometer inorganic filler is selected from least a in nano particle and nano whisker, specifically is selected from SiO
2, Si
3N
4, at least a in SiC and BN;
The mass ratio of described hybrid resin cured article and fiber is 100:100-200, is specially 100:107;
The mass ratio of described hybrid resin cured article, fiber and nanometer inorganic filler is 100:100-200:0-50, and the quality of described nanometer inorganic filler is not 0, is specially 100:107:7.
The room temperature flexural strength of described hybrid resin based composites is 340-365MPa, and modulus in flexure is 22-24GPa, and interlaminar shear strength is 22-25MPa;
The flexural strength of 500 ℃ is 147-162MPa, and modulus in flexure is 21-22GPa, and interlaminar shear strength is 10-11MPa.
In addition, the hybrid resin based composites that the invention described above provides in the high temperature resistant and/or electromagnetic wave transparent material of preparation application and contain the high temperature resistant and/or electromagnetic wave transparent material of described hybrid resin based composites, also belong to protection scope of the present invention.
Compared with prior art, the invention has the advantages that: compare existing organic resin, hybrid resin of the present invention has better temperature tolerance, and the decomposition temperature in air and nitrogen is all higher than 500 ℃, and 500 ℃ of atmospheric oxidation 1h resins are residual heavy higher than 70%; Compare existing inorganic resin, adopt the quartz fiber reinforced composite material good mechanical properties of hybrid resin preparation of the present invention, more than room temperature flexural strength 300MPa, 500 ℃ of flexural strengths of high temperature reach 150MPa.
In addition, hybrid resin processing performance provided by the invention is good, and solidification value is low, and is heated to certain temperature, and viscosity is low, good fluidity, and matrix material can adopt the molding modes such as mold pressing, RTM; Adopt in the prepared matrix material room temperature to 500 of hybrid resin of the present invention ℃, 1-12GHz scope dielectric properties excellent, specific inductivity is below 3.25, dielectric loss is below 0.012, and it is little to vary with temperature rate, can meet the application requiring of high temperature, short time, in high temperature wave transparent field, have extraordinary application prospect.
Description of drawings
Fig. 1 is the thermogravimetric curve of hybrid resin cured article in air and nitrogen in embodiment 1.
Fig. 2 is specific inductivity and the dielectric loss of matrix material in room temperature wideband 1-12GHz scope in embodiment 5.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
In following embodiment the methyl ethylene polysilazane resin of ownership formula I used is all available from Institute of Chemistry, Academia Sinica, production code member: PSN1, n=200 in structural formula;
Wherein, X is ownership formula II(used
) compound 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile, all available from Sigma Aldrich company, production code member S141208.
The preparation of embodiment 1 hybrid resin and cured article
One, drying 100mL beaker, add the polysilazane of compound methyl ethylene shown in formula I resin 10g, the 4-[3-of compound shown in formula II (3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 1g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, No. CAS: 78-67-1) 0.5g, after room temperature magnetic agitation reaction 10min, add acetone 50mL, proceeded blending reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtain hybrid resin A.Adopt Fourier infrared spectrum to confirm that hybrid resin A is at 2232cm
-1And 3405cm
-1Place has the charateristic avsorption band of C ≡ N and NH; Adopt differential scanning calorimeter DSC to confirm that hybrid resin A fusing point is 134 ℃, the curing reaction starting temperature is 200 ℃.
Hybrid resin A is transferred to baking oven, rises to 200 ℃ with 3 ℃/min temperature rise rate, and is incubated 5 hours, with 5 ℃/min, is down to room temperature, obtains hybrid resin A cured article.
Adopt the thermal weight loss behavior of thermal gravimetric analyzer TGA test cured article in air and nitrogen, Range of measuring temp is 30-1000 ℃, and temperature rise rate is 10 ℃/min, and analytical results shows its temperature T of weightless 5 percent
d5Being 492 ℃ in air, is 501 ℃ in nitrogen, and 1000 ℃ of residual focusing in air are 82%, are 84%(accompanying drawing 1 in nitrogen).
The preparation of embodiment 2 hybrid resins and cured article
One, drying 100mL beaker, add methyl ethylene polysilazane resin 10g, and 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 2g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, No. CAS: 78-67-1) 0.5g, the room temperature magnetic agitation, after reaction 10min, add acetone 70mL, continue reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtain hybrid resin B.
Be transferred to baking oven, rise to 200 ℃ with 3 ℃/min temperature rise rate, and be incubated 5 hours, with 5 ℃/min, be down to room temperature, obtain hybrid resin B cured article.
This hybrid resin cured article in air and nitrogen thermogravimetric curve and embodiment 1 acquired results without substance difference, repeat no more.
The preparation of embodiment 3 hybrid resins and cured article
One, drying 200ml beaker, add methyl ethylene polysilazane resin 10g, and 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 3g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, No. CAS: 78-67-1) 0.5g, magnetic agitation, in reaction 10min, add acetone 70mL, continue reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtain hybrid resin C.
Be transferred to baking oven, 3 ℃/min of temperature rise rate is set, 200 ℃ of outlet temperatures, and be incubated 5 hours, and be down to room temperature with 5 ℃/min, obtain hybrid resin C cured article.
This hybrid resin cured article in air and nitrogen thermogravimetric curve and embodiment 1 acquired results without substance difference, repeat no more.
The preparation of embodiment 4 hybrid resins and cured article
One, drying 200mL beaker, add methyl ethylene polysilazane resin 10g, and 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 4g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, No. CAS: 78-67-1) 0.5g, the room temperature magnetic agitation, after reaction 10min, add acetone 80mL, continue reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtain hybrid resin D.
Be transferred to baking oven, rise to 200 ℃ with 3 ℃/min temperature rise rate, and be incubated 5 hours, with 5 ℃/min, be down to room temperature, obtain hybrid resin D cured article.
This hybrid resin cured article in air and nitrogen thermogravimetric curve and embodiment 1 acquired results without substance difference, repeat no more.
The preparation of embodiment 5 hybrid resins and cured article
One, drying 200mL beaker, add methyl ethylene polysilazane resin 10g, and 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 5g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, No. CAS: 78-67-1) 0.5g, the room temperature magnetic agitation, after reaction 10min, add acetone 80mL, continue reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtain hybrid resin E.
Be transferred to baking oven, rise to 200 ℃ with 3 ℃/min temperature rise rate, and be incubated 5 hours, with 5 ℃/min, be down to room temperature, obtain hybrid resin E cured article.
This hybrid resin cured article in air and nitrogen thermogravimetric curve and embodiment 1 acquired results without substance difference, repeat no more.
The preparation of embodiment 6 hybrid resins and cured article
One, drying 100mL beaker, add methyl ethylene polysilazane resin 10g, and 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 1g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, No. CAS: 78-67-1) 0.5g, the room temperature magnetic agitation, after reaction 10min, add acetone 50mL, continue reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtain hybrid resin F.
Be transferred to baking oven, rise to 220 ℃ with 3 ℃/min temperature rise rate, and be incubated 5 hours, with 5 ℃/min, be down to room temperature, obtain hybrid resin F cured article.
This hybrid resin cured article in air and nitrogen thermogravimetric curve and embodiment 1 acquired results without substance difference, repeat no more.
The preparation of embodiment 7 hybrid resins and cured article
One, drying 100mL beaker, add methyl ethylene polysilazane resin 10g, and 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 1g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, No. CAS: 78-67-1) 0.5g, the room temperature magnetic agitation, after reaction 10min, add acetone 50mL, continue reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtain hybrid resin.
Be transferred to baking oven, rise to 240 ℃ with 3 ℃/min temperature rise rate, and be incubated 5 hours, with 5 ℃/min, be down to room temperature, obtain hybrid resin G cured article.
This hybrid resin cured article in air and nitrogen thermogravimetric curve and embodiment 1 acquired results without substance difference, repeat no more.
The preparation of embodiment 8 hybrid resin base wave-penetrating composite materials
Adopt the hybrid resin A cured article 15g in embodiment 1, with acetone, make solvent, be mixed with massfraction and be 50% resin impregnation liquid, quartz fabric is cut into the size of 10cm * 10cm, totally 20, amount to 16g, after dipping dries, neatly overlay in mould, be transferred to press, carry out compression molding.The highest forming pressure 1MPa, 250 ℃ of top temperatures.Obtain composite A after the cooling demoulding, wherein the resin quality mark 40%.
Adopt room temperature and the high-temperature mechanics intensity of universal testing machine test compound material, test result is: room temperature flexural strength 340MPa, modulus in flexure 22GPa, interlaminar shear strength 24MPa; 500 ℃ of flexural strength 154MPa, modulus in flexure 21GPa, interlaminar shear strength 10MPa.
Therefrom can find out, 500 ℃ of mechanical strengths are all more than 45%, and composite A shows excellent resistance to elevated temperatures; Adopt specific inductivity and the dielectric loss (accompanying drawing 2) of Agilent network vector analyser test compound materials A, therefrom can find out its specific inductivity in the 1-12GHz scope all in 3.1 left and right, dielectric loss between 0.0025-0.0083, illustrates that it has extraordinary wave penetrate capability.
The preparation of embodiment 9 hybrid resin based composites
Adopt the hybrid resin B cured article 15g in embodiment 2, adopt acetone to make solvent, be mixed with massfraction and be 50% resin impregnation liquid, quartz fabric is cut into the size of 10cm * 10cm, totally 20, amount to 16g, after dipping dries, neatly overlay in mould, be transferred to press, carry out compression molding.The highest forming pressure 1MPa, 250 ℃ of top temperatures.Obtain matrix material B through the cooling demoulding, wherein the resin quality mark 39%.
Adopt universal testing machine to test its room temperature flexural strength 354MPa, modulus in flexure 22GPa, interlaminar shear strength 23MPa; 500 ℃ of flexural strength 147MPa, modulus in flexure 21GPa, interlaminar shear strength 11MPa.
This matrix material in room temperature wideband 1-12GHz scope specific inductivity and dielectric loss and embodiment 8 without substantive difference, repeat no more.
The preparation of embodiment 10 hybrid resin based composites
Adopt the hybrid resin C cured article 15g in embodiment 3, adopt acetone to make solvent, be mixed with massfraction and be 50% resin impregnation liquid, quartz fabric is cut into the size of 10cm * 10cm, totally 20, amount to 16g, after dipping dries, neatly overlay in mould, be transferred to press, carry out compression molding.The highest forming pressure 1MPa, 250 ℃ of top temperatures.Obtain matrix material C through the cooling demoulding, wherein the resin quality mark 40%.
Adopt universal testing machine to test its room temperature flexural strength 358MPa, modulus in flexure 22GPa, interlaminar shear strength 25MPa; 500 ℃ of flexural strength 155MPa, modulus in flexure 22GPa, interlaminar shear strength 10MPa.
This matrix material in room temperature wideband 1-12GHz scope specific inductivity and dielectric loss and embodiment 8 without substantive difference, repeat no more.
The preparation of embodiment 11 hybrid resin based composites
Adopt the hybrid resin A cured article 15g in embodiment 1, adopt acetone to make solvent, be mixed with massfraction and be 50% resin impregnation liquid, then add 1g nanometer SiO in steeping fluid
2, ultra-sonic dispersion 1 hour.Quartz fabric is cut into the size of 10cm * 10cm, and totally 20, amount to 16g, after dipping dries, neatly overlay in mould, be transferred to press, carry out compression molding.The highest forming pressure 1MPa, 250 ℃ of top temperatures.Obtain matrix material D through the cooling demoulding, wherein the resin quality mark 42%.
Adopt universal testing machine to test its room temperature flexural strength 360MPa, modulus in flexure 24GPa, interlaminar shear strength 22MPa; 500 ℃ of flexural strength 160MPa, modulus in flexure 21GPa, interlaminar shear strength 10MPa.
This matrix material in room temperature wideband 1-12GHz scope specific inductivity and dielectric loss and embodiment 8 without substantive difference, repeat no more.
The preparation of embodiment 12 hybrid resin base wave-penetrating composite materials
Adopt the hybrid resin A cured article 15g in embodiment 1, adopt acetone to make solvent, be mixed with massfraction and be 50% resin impregnation liquid, then add 1g Si in steeping fluid
3N
4Whisker, ultra-sonic dispersion 1 hour.Quartz fabric is cut into the size of 10cm * 10cm, and totally 20, amount to 16g, after dipping dries, neatly overlay in mould, be transferred to press, carry out compression molding.The highest forming pressure 1MPa, 250 ℃ of top temperatures.Obtain matrix material D through the cooling demoulding, wherein the resin quality mark 42%.
Adopt universal testing machine to test its room temperature flexural strength 365MPa, modulus in flexure 24GPa, interlaminar shear strength 24MPa; 500 ℃ of flexural strength 162MPa, modulus in flexure 21GPa, interlaminar shear strength 11MPa.
This matrix material in room temperature wideband 1-12GHz scope specific inductivity and dielectric loss and embodiment 8 without substantive difference, repeat no more.
Claims (10)
1. method for preparing hybrid resin, comprise the steps: to add successively bi-phthalonitrile resin shown in polysilazane resin shown in formula I, formula II and solidifying agent in solvent, carry out blending reaction after mixing, react the complete solvent for use of removing, obtain described hybrid resin;
Formula I
In described formula I, R
1And R
2Identical or different, and all be selected from the aliphatics of C1～C6 and any one in aromatic alkyl;
N is 3～1000;
Formula II
In described formula II, X is any one in following group:
2. method according to claim 1 is characterized in that: in described formula I, and R
1And R
2All be selected from any one in methyl, ethyl, propyl group, phenyl, allyl group and vinyl;
N is 200;
Shown in polysilazane resin shown in described formula I and formula II, the mass ratio of bi-phthalonitrile resin is 100:5-100, is specially 100:10-50;
In described blending reaction step, temperature is room temperature, and the time is 0.5-15 hour, is specially 1-3 hour;
Described solvent is selected from METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide, N, dinethylformamide, N, at least a in N-diethylformamide, N-N-Methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide (DMSO), methylene dichloride, chloroform, tetrahydrofuran (THF) and acetone;
The consumption of described solvent be bi-phthalonitrile resin quality shown in polysilazane resin shown in formula I and formula II and 1-5 doubly, be specially 2-4 doubly.
3. method according to claim 1 and 2, it is characterized in that: described method also comprises the steps: to add solidifying agent in reaction system before described blending reaction step;
Described solidifying agent is selected from platinum catalyst, naphthenate, carboxylate salt, aminated compounds, peroxide catalyst, azo catalyzer, organo-tin compound and organic titanic compound at least a;
Wherein, described platinum catalyst is specially 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) or Karstedt catalyzer;
Described naphthenate and described carboxylate salt are specially naphthenate or the carboxylate salt of lead, zinc, cobalt, iron or the cerium of following element;
Described aminated compounds is specially methylamine, dimethylamine, ethamine, diethylamine, triethylamine, propylamine, dipropyl amine or butylamine;
Described peroxide catalyst is specially dicumyl peroxide;
Described azo catalyzer is specially Diisopropyl azodicarboxylate;
Described organo-tin compound is specially dibutyl tin laurate or stannous octoate;
Described organic titanic compound is specially tetrabutyl titanate;
The add-on of described solidifying agent is the 0.1%-20% of polysilazane resin quality shown in described formula I, is specially 5%.
4. the hybrid resin for preparing of the arbitrary described method of claim 1-3.
5. a method for preparing the hybrid resin cured article, comprise the steps: the described hybrid resin of claim 4 is warming up to 150 ℃-300 ℃ by room temperature, after being incubated 3 hours-15 hours, is cooled to room temperature, obtains described hybrid resin cured article.
6. method according to claim 5 is characterized in that: in described heating step, temperature rise rate is 1 ℃/min-15 ℃/min, is specially 3 ℃/min;
In described cooling step, rate of temperature fall is 1 ℃/min-15 ℃/min, is specially 5 ℃/min.
7. the hybrid resin cured article for preparing of the described method of claim 5 or 6.
8. hybrid resin based composites, by the described hybrid resin cured article of claim 7 and fibrous;
Or by the described hybrid resin cured article of claim 7, fiber and nanometer inorganic filler, formed.
9. material according to claim 8, it is characterized in that: described fiber is quartz textile, specifically is selected from least a in silica fiber cloth and three-dimensional quartz cloth;
Described nanometer inorganic filler is selected from least a in nano particle and nano whisker, specifically is selected from SiO
2, Si
3N
4, at least a in SiC and BN;
The mass ratio of described hybrid resin cured article and fiber is 100:100-200;
The mass ratio of described hybrid resin cured article, fiber and nanometer inorganic filler is 100:100-200:0-50, and the quality of described nanometer inorganic filler is not 0;
The room temperature flexural strength of described hybrid resin based composites is 340-365MPa, and modulus in flexure is 22-24GPa, and interlaminar shear strength is 22-25MPa;
The flexural strength of 500 ℃ is 147-162MPa, and modulus in flexure is 21-22GPa, and interlaminar shear strength is 10-11MPa.
10. the application of the described hybrid resin based composites of claim 8 or 9 in preparing high temperature resistant and/or electromagnetic wave transparent material;
High temperature resistant and/or the electromagnetic wave transparent material that contains the described hybrid resin based composites of claim 8 or 9.
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| CN110818896A (en) * | 2018-08-07 | 2020-02-21 | 中国科学院化学研究所 | Low-dielectric-loss phthalonitrile resin, cured resin thereof, and preparation method and application thereof |
| CN111499866A (en) * | 2020-06-04 | 2020-08-07 | 哈尔滨工业大学 | Preparation method of high-efficiency catalytic curing phenylacetylene-terminated polyimide resin system |
| CN111748205A (en) * | 2020-07-07 | 2020-10-09 | 山东非金属材料研究所 | High-temperature-resistant wave-transparent hybrid resin system suitable for wet winding and preparation method thereof |
| US10913822B2 (en) | 2016-10-31 | 2021-02-09 | Lg Chem, Ltd. | Compound |
| CN113292851A (en) * | 2020-02-21 | 2021-08-24 | 中国科学院化学研究所 | High-temperature-resistant hybrid phthalonitrile resin and preparation method and application thereof |
| CN113754904A (en) * | 2021-10-19 | 2021-12-07 | 中国电子科技集团公司第二十研究所 | Quartz fiber/modified cyanate composite material and preparation method and application thereof |
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| CN101981134A (en) * | 2008-02-05 | 2011-02-23 | 原子能和替代能源委员会 | Hybrid organic-inorganic material, optical thin layer made of said material, optical material containing same, and method for making same |
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| CN101981134A (en) * | 2008-02-05 | 2011-02-23 | 原子能和替代能源委员会 | Hybrid organic-inorganic material, optical thin layer made of said material, optical material containing same, and method for making same |
Cited By (11)
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| US10913822B2 (en) | 2016-10-31 | 2021-02-09 | Lg Chem, Ltd. | Compound |
| CN110818896A (en) * | 2018-08-07 | 2020-02-21 | 中国科学院化学研究所 | Low-dielectric-loss phthalonitrile resin, cured resin thereof, and preparation method and application thereof |
| CN110818896B (en) * | 2018-08-07 | 2021-06-01 | 中国科学院化学研究所 | Low-dielectric-loss phthalonitrile resin, cured resin thereof, and preparation method and application thereof |
| CN113292851A (en) * | 2020-02-21 | 2021-08-24 | 中国科学院化学研究所 | High-temperature-resistant hybrid phthalonitrile resin and preparation method and application thereof |
| CN113292851B (en) * | 2020-02-21 | 2022-03-01 | 中国科学院化学研究所 | High-temperature-resistant hybrid phthalonitrile resin and preparation method and application thereof |
| CN111499866A (en) * | 2020-06-04 | 2020-08-07 | 哈尔滨工业大学 | Preparation method of high-efficiency catalytic curing phenylacetylene-terminated polyimide resin system |
| CN111499866B (en) * | 2020-06-04 | 2022-02-18 | 哈尔滨工业大学 | Preparation method of high-efficiency catalytic curing phenylacetylene-terminated polyimide resin system |
| CN111748205A (en) * | 2020-07-07 | 2020-10-09 | 山东非金属材料研究所 | High-temperature-resistant wave-transparent hybrid resin system suitable for wet winding and preparation method thereof |
| CN111748205B (en) * | 2020-07-07 | 2022-09-23 | 山东非金属材料研究所 | High-temperature-resistant wave-transparent hybrid resin system suitable for wet winding and preparation method thereof |
| CN113754904A (en) * | 2021-10-19 | 2021-12-07 | 中国电子科技集团公司第二十研究所 | Quartz fiber/modified cyanate composite material and preparation method and application thereof |
| CN113754904B (en) * | 2021-10-19 | 2024-03-01 | 中国电子科技集团公司第二十研究所 | Quartz fiber/modified cyanate composite material and preparation method and application thereof |
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