CN103387748B - 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-reswave-transparent wave-transparent composite material and preparation method thereof, belong to field of material technology.
Background technology
Along with the development of aeronautical and space technology, the demand for the performance resins of resistant to elevated temperatures novel texture, function and structure function one is more and more urgent.Rocket, the aircraft such as guided missile are in the environment of thermal shocking in flight course, flight velocity is faster, surface temperature is higher, institute's heat-shock is more serious, such as when aircraft speed reaches 3 Mach, aircraft surface temperature reaches 400 DEG C, when aircraft speed reaches 4 Mach, its surface temperature is then more than 600 DEG C, thus require resin material high temperature (>600 DEG C) in short-term (in second) and low temperature (400-500 DEG C) long time (in minute) condition under can maintain its member integrity, there is certain mechanical strength, and it is anti-oxidant preferably, the performance of resistant to hydrolysis.In addition, the resin matrix as functional type wave-penetrating composite material must have again excellent dielectric properties, specifically, requires that its specific inductivity is between 1-4, and dielectric loss is between 0.0001-0.1, and dielectric constant with temperature change is less than 1%/100 DEG C.
Traditional organic resin, comprises polyimide, two maleinamide, epoxy and cyanaloc and namely occurred oxygenolysis before 500 DEG C, can not meet service requirements.Silicon-containing polymer, owing to having higher high-temperature stability, preferably weathering resistance and outstanding dielectric properties, is studied much and application.Russia has developed the silicone resin for High-temperature-reswave-transparent wave-transparent composite material, and in resin, add de-carbon metal oxide, avoids the decline of high temperature dielectric properties, and its resin grade is MK-9K.But organosilicon polymer is due to Si-O chain flexibility, and Intermolecular Forces is little, prepared composite materials property is on the low side.
Patent CN101891957A discloses a kind of method strengthening organic silicon resin-based High-temperature-reswave-transparent wave-transparent composite material mechanical property.Composite materials property is improved as nanometer reinforcing filler by the silsesquioxane POSS adding caged in silicone resin matrix.But its room temperature flexural intensity also only has about 150MPa.
Siliceous poly-aryne resin, due to the existence of alkynyl structure, substantially increases the degree of crosslinking of resin matrix, and thus resin shows excellent high-temperature stability, and the use temperature scope be expected at 500 DEG C 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, the reaction first between alkynyl is very fast, is very easy to cause sudden and violent gathering in solidification process, thus requires harsh to technology and equipment.Secondly, the existence of a large amount of alkynyl also causes high temperature Residual carbon high, and high temperature dielectric properties declines thereupon.
Summary of the invention
The object of the invention is to the deficiency overcoming existing resin system, a kind of new type resin system is provided, on the high-temperature stability basis keeping inorganic resin, improve its mechanical property by introducing organic resin, thus form the organic inorganic hybridization resin having mechanical property and resistance to elevated temperatures concurrently.
The method preparing hybrid resin provided by the invention, bi-phthalonitrile resin shown in the resin of polysilazane shown in formula I, formula II and solidifying agent is comprised the steps: to add successively in solvent, carry out blending reaction after mixing, react complete removing solvent for use, obtain described hybrid resin;
Formula I
In described formula I, R
1and R
2identical or different, and any one being all selected from the aliphatics of C1 ~ C6 and 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 methyl, ethyl, propyl group, phenyl, allyl group and vinyl any one;
N is 200;
In aforesaid method, shown in described formula I, the mass ratio of bi-phthalonitrile resin shown in polysilazane resin and formula II 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, at least one in dinethylformamide, N, N-diethylformamide, N-N-Methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide (DMSO), methylene dichloride, chloroform, tetrahydrofuran (THF) and acetone;
The consumption of described solvent for bi-phthalonitrile resin quality shown in the resin of polysilazane 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:, before described blending reaction step, in reaction system, to add solidifying agent;
Described solidifying agent is selected from least one in platinum catalyst, naphthenate, carboxylate salt, aminated compounds, peroxide catalyst, azo catalyzer, organo-tin compound and organic titanic compound;
Wherein, described platinum catalyst is specially 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) (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 the lead of following element, zinc, cobalt, iron or cerium;
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%.
Present invention also offers a kind of hybrid resin, this hybrid resin is to obtain according to aforementioned method preparation provided by the invention.
Present invention also offers a kind of method preparing hybrid resin cured article.The method to comprise the steps: described hybrid resin, by room temperature to 150 DEG C-300 DEG C, to be incubated after 3-15 hour, to be cooled to room temperature, obtain described hybrid resin cured article.
In heating step described in aforesaid method, temperature rise rate is 1-15 DEG C/min, is specially 3 DEG C/min; The final temperature of heating step is specially 200 DEG C, and soaking time is specially 5 hours;
In described cooling step, rate of temperature fall is 1-15 DEG C/min, is specially 5 DEG C/min.
Present invention also offers a kind of hybrid resin cured article, this hybrid resin cured article prepares according to the method described above and obtains.
Present invention also offers a kind of hybrid resin based composites, this matrix material is by aforementioned hybrid resin cured article provided by the invention and fibrous;
Or be made up of described hybrid resin cured article, fiber and nanometer inorganic filler.In above-mentioned matrix material, described fiber is quartz textile, is specifically selected from least one in quartz fiber cloth and three-dimensional quartz cloth;
Described nanometer inorganic filler is selected from least one in nano particle and nano whisker, is specifically selected from SiO
2, Si
3n
4, at least one 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 intensity 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 DEG C 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, at the application prepared in high temperature resistant and/or electromagnetic wave transparent material and the high temperature resistant and/or electromagnetic wave transparent material containing described hybrid resin based composites, also belongs 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 DEG C, and 500 DEG C of atmospheric oxidation 1h resins are residual heavy higher than 70%; Compare existing inorganic resin, adopt quartz fiber reinforced composite material good mechanical properties prepared by hybrid resin of the present invention, more than room temperature flexural intensity 300MPa, high temperature 500 DEG C of flexural strengths 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 mode such as mold pressing, RTM; Adopt dielectric properties within the scope of matrix material room temperature to 500 prepared by hybrid resin of the present invention DEG C, 1-12GHz excellent, specific inductivity less than 3.25, dielectric loss less than 0.012, and it is little to vary with temperature rate, the application requiring of high temperature, short time can be met, in high temperature wave transparent field, there is extraordinary application prospect.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric curve of hybrid resin cured article in air and nitrogen in embodiment 1.
Fig. 2 is the specific inductivity of matrix material within the scope of room temperature wideband 1-12GHz and dielectric loss in embodiment 5.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, 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 purchased 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 purchased from Sigma Aldrich company, production code member S141208.
The preparation of embodiment 1 hybrid resin and cured article
One, drying 100mL beaker, adds the vinyl of compounds methyl shown in formula I polysilazane resin 10g, the 4-of compound shown in formula II [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, after room temperature magnetic agitation reaction 10min, add acetone 50mL, proceed blending reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtains hybrid resin A.Hybrid resin A is at 2232cm to adopt Fourier infrared spectrum to confirm
-1and 3405cm
-1place has the charateristic avsorption band of C ≡ N and NH; Hybrid resin A fusing point is 134 DEG C to adopt differential scanning calorimeter DSC to confirm, curing reaction starting temperature is 200 DEG C.
Hybrid resin A is transferred to baking oven, rises to 200 DEG C, and is incubated 5 hours, be down to room temperature with 5 DEG C/min with 3 DEG C/min temperature rise rate, obtains hybrid resin A cured article.
Adopt thermal gravimetric analyzer TGA to test the thermal weight loss behavior of cured article in air and nitrogen, Range of measuring temp is 30-1000 DEG C, and temperature rise rate is 10 DEG C/min, and analytical results shows its temperature T of weightless 5 percent
d5being 492 DEG C in atmosphere, is 501 DEG C in nitrogen, 1000 DEG C residual heavy be 82% in atmosphere, be 84%(accompanying drawing 1 in nitrogen).
The preparation of embodiment 2 hybrid resin and cured article
One, drying 100mL beaker, adds methyl ethylene polysilazane resin 10g, 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 2g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, 0.5g No. CAS: 78-67-1), room temperature magnetic agitation, after reaction 10min, adds 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 DEG C with 3 DEG C/min temperature rise rate, and be incubated 5 hours, be down to room temperature with 5 DEG C/min, obtain hybrid resin B cured article.
The thermogravimetric curve of this hybrid resin cured article in air and nitrogen and embodiment 1 acquired results, without substance just difference, repeat no more.
The preparation of embodiment 3 hybrid resin and cured article
One, drying 200ml beaker, adds methyl ethylene polysilazane resin 10g, 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 3g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, 0.5g No. CAS: 78-67-1), magnetic agitation, in reaction 10min, adds acetone 70mL, continue reaction 1 hour, obtain homogeneous solution, removal of solvent under reduced pressure, obtain hybrid resin C.
Be transferred to baking oven, temperature rise rate 3 DEG C/min is set, outlet temperature 200 DEG C, and be incubated 5 hours, be down to room temperature with 5 DEG C/min, obtain hybrid resin C cured article.
The thermogravimetric curve of this hybrid resin cured article in air and nitrogen and embodiment 1 acquired results, without substance just difference, repeat no more.
The preparation of embodiment 4 hybrid resin and cured article
One, drying 200mL beaker, adds methyl ethylene polysilazane resin 10g, 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 4g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, 0.5g No. CAS: 78-67-1), room temperature magnetic agitation, after reaction 10min, adds 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 DEG C with 3 DEG C/min temperature rise rate, and be incubated 5 hours, be down to room temperature with 5 DEG C/min, obtain hybrid resin D cured article.
The thermogravimetric curve of this hybrid resin cured article in air and nitrogen and embodiment 1 acquired results, without substance just difference, repeat no more.
The preparation of embodiment 5 hybrid resin and cured article
One, drying 200mL beaker, adds methyl ethylene polysilazane resin 10g, 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 5g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, 0.5g No. CAS: 78-67-1), room temperature magnetic agitation, after reaction 10min, adds 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 DEG C with 3 DEG C/min temperature rise rate, and be incubated 5 hours, be down to room temperature with 5 DEG C/min, obtain hybrid resin E cured article.
The thermogravimetric curve of this hybrid resin cured article in air and nitrogen and embodiment 1 acquired results, without substance just difference, repeat no more.
The preparation of embodiment 6 hybrid resin and cured article
One, drying 100mL beaker, adds methyl ethylene polysilazane resin 10g, 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 1g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, 0.5g No. CAS: 78-67-1), room temperature magnetic agitation, after reaction 10min, adds 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 DEG C with 3 DEG C/min temperature rise rate, and be incubated 5 hours, be down to room temperature with 5 DEG C/min, obtain hybrid resin F cured article.
The thermogravimetric curve of this hybrid resin cured article in air and nitrogen and embodiment 1 acquired results, without substance just difference, repeat no more.
The preparation of embodiment 7 hybrid resin and cured article
One, drying 100mL beaker, adds methyl ethylene polysilazane resin 10g, 4-[3-(3,4-dicyano phenoxy group) phenoxy group] phthalonitrile 1g, solidifying agent: Diisopropyl azodicarboxylate (AIBN, traditional Chinese medicines chemical reagents corporation, 0.5g No. CAS: 78-67-1), room temperature magnetic agitation, after reaction 10min, adds 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 DEG C with 3 DEG C/min temperature rise rate, and be incubated 5 hours, be down to room temperature with 5 DEG C/min, obtain hybrid resin G cured article.
The thermogravimetric curve of this hybrid resin cured article in air and nitrogen and embodiment 1 acquired results, without substance just difference, repeat no more.
The preparation of embodiment 8 hybrid resin base wave-penetrating composite material
Adopt the hybrid resin A cured article 15g in embodiment 1, with acetone as solvent, be mixed with the resin impregnation liquid that massfraction is 50%, quartz fabric is cut into the size of 10cm × 10cm, totally 20, amount to 16g, after dipping dries, neatly stack in a mold, be transferred to press, carry out compression molding.The highest forming pressure 1MPa, top temperature 250 DEG C.Composite A is obtained, wherein resin quality mark 40% after the cooling demoulding.
Adopt room temperature and the high-temperature mechanics intensity of universal testing machine test compound material, test result is: room temperature flexural intensity 340MPa, modulus in flexure 22GPa, interlaminar shear strength 24MPa; 500 DEG C of flexural strength 154MPa, modulus in flexure 21GPa, interlaminar shear strength 10MPa.
Therefrom can find out, 500 DEG C 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 within the scope of 1-12GHz all about 3.1, 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 as solvent, be mixed with the resin impregnation liquid that massfraction is 50%, quartz fabric is cut into the size of 10cm × 10cm, totally 20, amount to 16g, after dipping dries, neatly stack in a mold, be transferred to press, carry out compression molding.The highest forming pressure 1MPa, top temperature 250 DEG C.Matrix material B is obtained, wherein resin quality mark 39% through the cooling demoulding.
Universal testing machine is adopted to test its room temperature flexural intensity 354MPa, modulus in flexure 22GPa, interlaminar shear strength 23MPa; 500 DEG C of flexural strength 147MPa, modulus in flexure 21GPa, interlaminar shear strength 11MPa.
The specific inductivity of this matrix material within the scope of room temperature wideband 1-12GHz 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 as solvent, be mixed with the resin impregnation liquid that massfraction is 50%, quartz fabric is cut into the size of 10cm × 10cm, totally 20, amount to 16g, after dipping dries, neatly stack in a mold, be transferred to press, carry out compression molding.The highest forming pressure 1MPa, top temperature 250 DEG C.Matrix material C is obtained, wherein resin quality mark 40% through the cooling demoulding.
Universal testing machine is adopted to test its room temperature flexural intensity 358MPa, modulus in flexure 22GPa, interlaminar shear strength 25MPa; 500 DEG C of flexural strength 155MPa, modulus in flexure 22GPa, interlaminar shear strength 10MPa.
The specific inductivity of this matrix material within the scope of room temperature wideband 1-12GHz 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 as solvent, be mixed with the resin impregnation liquid that massfraction is 50%, then in steeping fluid, add 1g Nano-meter SiO_2
2, ultrasonic disperse 1 hour.Quartz fabric is cut into the size of 10cm × 10cm, totally 20, amounts to 16g, after dipping dries, neatly stacks in a mold, is transferred to press, carry out compression molding.The highest forming pressure 1MPa, top temperature 250 DEG C.Matrix material D is obtained, wherein resin quality mark 42% through the cooling demoulding.
Universal testing machine is adopted to test its room temperature flexural intensity 360MPa, modulus in flexure 24GPa, interlaminar shear strength 22MPa; 500 DEG C of flexural strength 160MPa, modulus in flexure 21GPa, interlaminar shear strength 10MPa.
The specific inductivity of this matrix material within the scope of room temperature wideband 1-12GHz and dielectric loss and embodiment 8, without substantive difference, repeat no more.
The preparation of embodiment 12 hybrid resin base wave-penetrating composite material
Adopt the hybrid resin A cured article 15g in embodiment 1, adopt acetone as solvent, be mixed with the resin impregnation liquid that massfraction is 50%, then in steeping fluid, add 1g Si
3n
4whisker, ultrasonic disperse 1 hour.Quartz fabric is cut into the size of 10cm × 10cm, totally 20, amounts to 16g, after dipping dries, neatly stacks in a mold, is transferred to press, carry out compression molding.The highest forming pressure 1MPa, top temperature 250 DEG C.Matrix material D is obtained, wherein resin quality mark 42% through the cooling demoulding.
Universal testing machine is adopted to test its room temperature flexural intensity 365MPa, modulus in flexure 24GPa, interlaminar shear strength 24MPa; 500 DEG C of flexural strength 162MPa, modulus in flexure 21GPa, interlaminar shear strength 11MPa.
The specific inductivity of this matrix material within the scope of room temperature wideband 1-12GHz and dielectric loss and embodiment 8, without substantive difference, repeat no more.
Claims (15)
1. prepare the method for hybrid resin for one kind, bi-phthalonitrile resin shown in the resin of polysilazane shown in formula I, formula II and solidifying agent is comprised the steps: to add successively in solvent, carry out blending reaction after mixing, react complete removing solvent for use, obtain described hybrid resin;
In described formula I, R
1and R
2identical or different, and any one being all selected from the aliphatics of C1 ~ C6 and aromatic alkyl;
N is 3 ~ 1000;
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, R
1and R
2all be selected from methyl, ethyl, propyl group, phenyl, allyl group and vinyl any one;
N is 200;
Shown in described formula I, the mass ratio of bi-phthalonitrile resin shown in polysilazane resin and formula II is 100:5-100;
In described blending reaction step, temperature is room temperature, and the time is 0.5-15 hour;
Described solvent is selected from METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide, N, at least one in dinethylformamide, N, N-diethylformamide, N-N-Methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide (DMSO), methylene dichloride, chloroform, tetrahydrofuran (THF) and acetone;
The consumption of described solvent for bi-phthalonitrile resin quality shown in the resin of polysilazane shown in formula I and formula II and 1-5 doubly.
3. method according to claim 2, is characterized in that: shown in described formula I, the mass ratio of bi-phthalonitrile resin shown in polysilazane resin and formula II is 100:10-50;
In described blending reaction step, the time is 1-3 hour;
The consumption of described solvent for bi-phthalonitrile resin quality shown in the resin of polysilazane shown in formula I and formula II and 2-4 doubly.
4., according to described method arbitrary in claim 1-3, it is characterized in that: described method also comprises the steps:, before described blending reaction step, in reaction system, to add solidifying agent;
Described solidifying agent is selected from least one in platinum catalyst, naphthenate, carboxylate salt, aminated compounds, peroxide catalyst, azo catalyzer, organo-tin compound and organic titanic compound;
The 0.1%-20% that the add-on of described solidifying agent is polysilazane resin quality shown in described formula I.
5. method according to claim 4, is characterized in that: described platinum catalyst is 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) or Karstedt catalyzer;
Described naphthenate and described carboxylate salt are naphthenate or the carboxylate salt of the lead of following element, zinc, cobalt, iron or cerium;
Described aminated compounds is methylamine, dimethylamine, ethamine, diethylamine, triethylamine, propylamine, dipropyl amine or butylamine;
Described peroxide catalyst is dicumyl peroxide;
Described azo catalyzer is Diisopropyl azodicarboxylate;
Described organo-tin compound is dibutyl tin laurate or stannous octoate;
Described organic titanic compound is tetrabutyl titanate;
The add-on of described solidifying agent is 5% of polysilazane resin quality shown in described formula I.
6. the hybrid resin for preparing of the arbitrary described method of claim 1-5.
7. prepare a method for hybrid resin cured article, to comprise the steps: hybrid resin described in claim 6, by room temperature to 150 DEG C-300 DEG C, to be incubated after 3 hours-15 hours, to be cooled to room temperature, obtain described hybrid resin cured article.
8. method according to claim 7, is characterized in that: in described heating step, temperature rise rate is 1 DEG C/and min-15 DEG C/min;
In described cooling step, rate of temperature fall is 1 DEG C/min-15 DEG C/min.
9. method according to claim 8, is characterized in that: in described heating step, and temperature rise rate is 3 DEG C/min;
In described cooling step, rate of temperature fall is 5 DEG C/min.
10. the hybrid resin cured article that in claim 7-9, arbitrary described method prepares.
11. 1 kinds of hybrid resin based composites, by hybrid resin cured article described in claim 10 and fibrous;
Or be made up of hybrid resin cured article, fiber and nanometer inorganic filler described in claim 10.
12. materials according to claim 11, is characterized in that: described fiber is quartz textile;
Described nanometer inorganic filler is selected from least one in nano particle and nano whisker;
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 intensity 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 DEG C is 147-162MPa, and modulus in flexure is 21-22GPa, and interlaminar shear strength is 10-11MPa.
13. materials according to claim 12, is characterized in that: described fiber is selected from least one in quartz fiber cloth and three-dimensional quartz cloth;
Described nanometer inorganic filler is SiO
2, Si
3n
4, at least one in SiC and BN.
In 14. claim 11-13, arbitrary described hybrid resin based composites is preparing the application in high temperature resistant and/or electromagnetic wave transparent material.
15. high temperature resistant and/or electromagnetic wave transparent materials containing arbitrary described hybrid resin based composites in claim 11-13.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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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| 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 |
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