CN113024833A - Epoxy end group fluorine-containing hyperbranched structure interface compatilizer and preparation method thereof, and wave-transparent composite material and preparation method thereof - Google Patents
Epoxy end group fluorine-containing hyperbranched structure interface compatilizer and preparation method thereof, and wave-transparent composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an epoxy end group fluorine-containing hyperbranched structure interface compatilizer and a preparation method thereof, a wave-transparent composite material and a preparation method thereof, and belongs to the technical field of composite material preparation. The epoxy end group fluorine-containing hyperbranched structure interface compatilizer provided by the invention is hyperbranched polymer molecules, and epoxy groups of the hyperbranched polymer molecules can generate copolymerization reaction with-OCN groups in cyanate ester resin, so that the cross-linking point distance is increased, and the mechanical property of the cyanate ester resin is improved. The introduction of the fluorine-containing group can effectively reduce the molecular polarizability of the cyanate ester resin, thereby improving the dielectric properties of the cyanate ester resin cured product. Therefore, the epoxy end group fluorine-containing hyperbranched structure interface compatilizer can introduce a fluorine-containing group, an epoxy end group, a PBO-like structure and a special topological structure of hyperbranched molecules into a curing network of the cyanate ester resin, so that the mechanical property, the dielectric property and the insulating property of the PBO fiber/cyanate ester resin wave-transmitting composite material are synchronously improved.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to an epoxy end group fluorine-containing hyperbranched structure interface compatilizer and a preparation method thereof, and a wave-transparent composite material and a preparation method thereof.
Background
The Cyanate (CE) resin has excellent dielectric properties (epsilon, 2.8-3.2), better heat resistance and dimensional stability, and is known to be one of the best candidate base materials of the next-generation resin-based wave-transparent composite material. However, the highly crosslinked triazine ring structure makes the cured CE resin have large brittleness and unsatisfactory mechanical properties, and the dielectric properties of the cured CE resin have a gap from the application requirements of high-performance wide-frequency-band resin-based wave-transmitting composite materials.
Poly-p-Phenylene Benzobisoxazole (PBO) fibers have a relatively low density (1.53 g/cm)3) Excellent dielectric properties (epsilon, 3.0; tan delta, 0.001), excellent mechanical properties (tensile strength and modulus of 5.8GPa and 270GPa, respectively) and excellent heat resistance (initial thermal decomposition temperature of 650 ℃). However, the surface of the PBO fiber is very smooth and has a high degree of chemical inertness, so that the mechanical properties (such as interlaminar shear strength (ILSS)) of the composite material prepared by using the PBO fiber as a reinforcing phase are poor, and the application of the PBO fiber in a high-performance resin-based wave-transmitting material is limited.
In order to improve the mechanical properties of resin-based wave-transmitting materials, a novel interfacial compatilizer has been developed in the prior art to promote the compatibility between PBO fibers and a resin matrix, so as to achieve the purpose of improving the properties of the resin-based wave-transmitting materials, such as: wu et al (ShaohuaWu, Chuncheng Li, Zihuayu, Rong Link, Yaonan Xiao, Liuchun Zheng, Jianjian Liu and Bo Zhuang. nondestructive strand to interactive strand and PBO/epoxy composites [ J ] J].ACS Applied Materials&Interfaces,2020,12(40): 45383-45393) designs and synthesizes a PBO fiber interface compatilizer 2, 6-bis (2-hydroxy-4-aminophenyl) benzobisoxazole (HABO), and the PBO fiber interface compatilizer is mixed with amino functional silicon dioxide (SiO)2-NH2) And epoxy resin, and preparing the modified PBO fiber by a simple coating method. The results show that the wettability, the surface roughness and the compatibility with a polymer matrix of the modified PBO fiber are all obviously improved; meanwhile, the mechanical and thermal properties of the PBO fiber are not damaged, the ILSS of the corresponding composite material is 29.2MPa, and the ILSS is improved by 40.4 percent compared with the ILSS of the unmodified PBO fiber/epoxy resin composite material by 20.8 MPa.
However, the prior art has little work on the interfacial compatibility of cyanate ester and PBO systems.
Disclosure of Invention
In view of the above, the present invention provides an epoxy-terminated fluorine-containing hyperbranched interfacial compatibilizer, a preparation method thereof, a wave-transparent composite material, and a preparation method thereof. The epoxy end group fluorine-containing hyperbranched structure interface compatilizer provided by the invention can obviously improve the compatibility of PBO fiber and cyanate resin base, thereby improving the mechanical property of thermosetting resin.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an epoxy end group fluorine-containing hyperbranched structure interface compatilizer, which has a structure shown in a formula I:
in the formula I, m and n are positive integers; the interfacial compatilizer with the epoxy end group fluorine-containing hyperbranched structure has an intrinsic viscosity coefficient of 0.160-0.168 g/dL at 25 ℃.
The invention provides a preparation method of an epoxy end group fluorine-containing hyperbranched structure interface compatilizer, which comprises the following steps:
mixing tert-butyldimethylchlorosilane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, first triethylamine and a first organic solvent, and carrying out a silyl group protection reaction to obtain a silyl group protection reaction solution;
dropwise adding trimesoyl chloride into the silane-based protective reaction liquid to carry out polycondensation reaction to obtain polycondensation reaction liquid;
and mixing the polycondensation reaction liquid with second triethylamine and glycidol in sequence, and carrying out end group modification reaction to obtain the epoxy end group fluorine-containing hyperbranched structure interface compatilizer.
Preferably, the mass ratio of the tert-butyldimethylsilyl chloride to the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane to the first triethylamine to the first organic solvent is (0.7-0.8): (0.34-0.38): (0.46-0.6): (4-6); the silane-based protection reaction is carried out under the atmosphere of argon; the temperature of the silane group protection reaction is 15-35 ℃, and the time is 20-28 h.
Preferably, the mass ratio of the trimesoyl chloride to the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is (0.262-0.268): (0.34-0.38); the polycondensation reaction is carried out under the condition of ice-water bath; the time of the polycondensation reaction is 24 hours.
Preferably, the mass ratio of the second triethylamine, the glycidol and the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is (0.15-0.3): (0.1-0.2): (0.34-0.38); the temperature of the end group modification reaction is room temperature, and the time is 20-28 h.
The invention also provides a wave-transparent composite material which comprises the following components in parts by weight:
40-60 parts of PBO fiber, 0.28-0.38 part of interfacial compatilizer and 39.72-59.62 parts of cyanate ester resin;
the interface compatilizer is the epoxy end group fluorine-containing hyperbranched structure interface compatilizer in the technical scheme or the epoxy end group fluorine-containing hyperbranched structure interface compatilizer obtained by the preparation method in the technical scheme.
The invention also provides a preparation method of the wave-transparent composite material in the technical scheme, which comprises the following steps:
mixing the interfacial compatilizer and a second organic solvent, and then mixing the mixture with cyanate ester resin for prepolymerization to obtain a prepolymer;
sequentially mixing the prepolymer with a third organic solvent and di-n-butyltin dilaurate to obtain a prepreg;
and mixing the prepreg and the PBO fiber, and performing mould pressing and curing after the third organic solvent is volatilized to obtain the wave-transparent composite material.
Preferably, the prepolymerization temperature is 120-150 ℃ and the time is 15-25 min.
Preferably, the volume ratio of the prepolymer to the third organic solvent is (0.8-1.2): (0.9 to 1.1); the volume of the di-n-butyltin dilaurate is 0.4-0.6% of that of the cyanate ester resin.
Preferably, the pressure of the mould pressing solidification is 5-10 MPa, and the mould pressing solidification comprises first solidification, second solidification, third solidification and fourth solidification which are sequentially carried out; the temperature of the first curing is 140-160 ℃, the time is 1h, the temperature of the second curing is 170-180 ℃, the time is 2h, the temperature of the third curing is 190-210 ℃, the time is 5-6 h, and the temperature of the fourth curing is 220-230 ℃, and the time is 2 h.
The invention provides an epoxy end group fluorine-containing hyperbranched structure interface compatilizer, which has a structure shown in a formula I:
in the formula I, m and n are positive integers; the interfacial compatilizer with the epoxy end group fluorine-containing hyperbranched structure has an intrinsic viscosity coefficient of 0.160-0.168 g/dL at 25 ℃.
The epoxy end group fluorine-containing hyperbranched structure interface compatilizer provided by the invention is hyperbranched polymer molecules, and linear units in the hyperbranched polymer molecules are used as a cavity structure, so that the free volume of a resin material can be increased, and the number of polarized molecules in unit volume is reduced, thereby improving the dielectric property; and the hyperbranched polymer has a special topological structure and rich terminal active groups, and can obviously improve the mechanical property of the resin. The epoxy group can generate copolymerization reaction with-OCN group in the cyanate ester resin, thereby increasing the distance between crosslinking points and improving the mechanical property of the cyanate ester resin. In addition, the introduction of the fluorine-containing group can effectively reduce the molecular polarizability of the cyanate ester resin, thereby improving the dielectric properties of the cyanate ester resin cured product. Therefore, the epoxy end group fluorine-containing hyperbranched structure interface compatilizer can introduce a fluorine-containing group, an epoxy end group, a PBO-like structure and a special topological structure of hyperbranched molecules into a curing network of the cyanate ester resin, so that the mechanical property, the dielectric property and the insulating property of the PBO fiber/cyanate ester resin wave-transmitting composite material are synchronously improved.
The invention also provides a preparation method of the epoxy end group fluorine-containing hyperbranched structure interface compatilizer. The invention is based on polycondensation and end group modification reaction, adopts a one-pot method to directly prepare the epoxy end group fluorine-containing hyperbranched structure interface compatilizer, has simple operation and is suitable for industrial development.
The invention also provides a wave-transparent composite material which comprises the following components in parts by weight: 40-60 parts of PBO fiber, 0.28-0.38 part of interfacial compatilizer and 39.72-59.62 parts of cyanate ester resin; the interface compatilizer is the epoxy end group fluorine-containing hyperbranched structure interface compatilizer in the technical scheme or the epoxy end group fluorine-containing hyperbranched structure interface compatilizer obtained by the preparation method in the technical scheme. According to the invention, through the epoxy end group fluorine-containing hyperbranched structure interface compatilizer, a fluorine-containing group, an epoxy end group, a PBO-like structure and a special hyperbranched molecular topological structure can be introduced into a curing network of the cyanate ester resin, so that the mechanical property, the dielectric property and the insulating property of the PBO fiber/cyanate ester resin wave-transparent composite material are synchronously improved.
The invention also provides a preparation method of the wave-transparent composite material, which is simple to operate and can fully compound the PBO fiber, the interface compatilizer and the cyanate resin.
The data of the examples show that: the epsilon and tan delta values of the obtained wave-transparent composite material at 1MHz are respectively 2.65 and 0.003, which are improved by 12.8 percent and 49.1 percent compared with the unmodified PBO fiber/bisphenol A cyanate ester resin laminated composite material (the epsilon and tan delta are respectively 3.04 and 0.0059); excellent mechanical properties (flexural strength and interlaminar shear strength (ILSS) of 634.9MPa and 46.9MPa respectively; corresponding volume resistivity and breakdown voltage of 4.93X 10 respectively15Omega cm and 25.38 kV/mm.
Drawings
FIG. 1 shows that the epoxy-terminated fluorine-containing hyperbranched structure interface compatilizer obtained in example 11H NMR spectrum;
FIG. 2 shows that the epoxy-terminated fluorine-containing hyperbranched structure interface compatilizer obtained in example 113C NMR spectrum;
FIG. 3 is an enlarged view within the circular dashed box of FIG. 2;
FIG. 4 is a FT-IR spectrum of the epoxy-terminated fluorine-containing hyperbranched structure interfacial compatilizer obtained in example 1.
Detailed Description
The invention provides an epoxy end group fluorine-containing hyperbranched structure interface compatilizer, which has a structure shown in a formula I:
in the formula I, m and n are positive integers; the interfacial compatilizer with the epoxy end group fluorine-containing hyperbranched structure has an intrinsic viscosity coefficient of 0.160-0.168 g/dL at 25 ℃.
In the invention, the intrinsic viscosity coefficient of the interfacial compatilizer with the epoxy end group fluorine-containing hyperbranched structure at 25 ℃ is preferably 0.162-0.168 g/dL.
The invention also provides a preparation method of the epoxy end group fluorine-containing hyperbranched structure interface compatilizer, which comprises the following steps:
mixing tert-butyldimethylchlorosilane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, first triethylamine and a first organic solvent, and carrying out a silyl group protection reaction to obtain a silyl group protection reaction solution;
dropwise adding trimesoyl chloride into the silane-based protective reaction liquid to carry out polycondensation reaction to obtain polycondensation reaction liquid;
and mixing the polycondensation reaction liquid with second triethylamine and glycidol in sequence, and carrying out end group modification reaction to obtain the epoxy end group fluorine-containing hyperbranched structure interface compatilizer.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
According to the invention, tert-butyldimethylsilyl chloride, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, first triethylamine and a first organic solvent are mixed to carry out a silyl group protection reaction, so as to obtain a silyl group protection reaction solution.
In the present invention, the first organic solvent is preferably N, N-dimethylformamide, N-methylpyrrolidone, or N, N-dimethylacetamide, more preferably N, N-dimethylformamide or N-methylpyrrolidone, and still more preferably N-methylpyrrolidone. In the present invention, the mass ratio of the tert-butyldimethylsilyl chloride, the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the first triethylamine and the first organic solvent is preferably (0.7 to 0.8): (0.34-0.38): (0.46-0.6): (4-6), more preferably (0.73-0.78): (0.35-0.38): (0.5-0.6): (5-6), more preferably 0.75: 0.36: 0.5: 6.
according to the invention, the mass ratio of the first organic solvent to the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane to the trimesoyl chloride is controlled, so that the finally obtained epoxy end group fluorine-containing hyperbranched structure interface compatilizer has a proper viscosity coefficient.
In the present invention, the silane group protecting reaction is preferably carried out under an argon atmosphere; the temperature of the silane group protection reaction is preferably 15-35 ℃, more preferably 20-30 ℃, more preferably 25 ℃, and the time is preferably 20-28 h, more preferably 22-24 h. In the present invention, the silane group protection reaction is preferably carried out under the condition of an oil bath.
In the present invention, the process of the silane group protection reaction is specifically: mixing tert-butyldimethylchlorosilane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, first triethylamine and a first organic solvent, introducing argon, sealing a reaction system, and carrying out a silane-based protection reaction; and the time for introducing the argon is 30-40 min.
After obtaining the silane-based protective reaction liquid, the invention adds trimesoyl chloride dropwise into the silane-based protective reaction liquid to carry out polycondensation reaction, thus obtaining the polycondensation reaction liquid.
In the present invention, the mass ratio of trimesoyl chloride to 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferably (0.262 to 0.268): (0.34 to 0.38), and more preferably 0.27: (0.35-0.38); the trimesoyl chloride is preferably used in the form of a trimesoyl chloride solution, the solvent of which is preferably a first organic solvent; the mass ratio of trimesoyl chloride (TMC) to the solvent in the trimesoyl chloride solution is preferably (0.262-0.268): (4-7), more preferably 0.27: (6-7).
In the invention, the dripping speed is preferably 30-60 drops/min; stirring the silane-based protective reaction liquid in the dropwise adding process of the trimesoyl chloride and placing the silane-based protective reaction liquid in an ice-water bath to maintain the condition of the polycondensation reaction; the rotating speed of the stirring is preferably 600-800 r/min. In the invention, the polycondensation reaction is preferably carried out under the conditions of nitrogen and ice water bath, and the time of the polycondensation reaction is preferably 20-28 h, and more preferably 24-26 h; the time of the polycondensation reaction is counted from the end of the dropwise addition of trimesoyl chloride.
After the polycondensation reaction liquid is obtained, the polycondensation reaction liquid is sequentially mixed with second triethylamine and glycidol to carry out terminal group modification reaction, and the epoxy terminal group fluorine-containing hyperbranched structure interface compatilizer is obtained.
In the present invention, the mass ratio of the second triethylamine, glycidol, and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferably (0.15 to 0.3): (0.1-0.2): (0.34-0.38), more preferably (0.2-0.3): (0.1-0.2): (0.35-0.38). In the present invention, the manner of mixing the polycondensation reaction liquid with the second triethylamine and the glycidol in this order is preferably: and adding the second triethylamine into the polycondensation reaction liquid, mixing, and then adding glycidol. In the invention, the polycondensation reaction liquid is stirred, and the stirring speed is preferably 800-1200 r/min; and preferably, mixing the second triethylamine and the polycondensation reaction liquid for 1-3 h.
In the present invention, the temperature of the terminal group modification reaction is preferably room temperature, i.e., neither additional heating nor additional cooling is required; the time of the end group modification reaction is preferably 20-28 h, and more preferably 24 h.
After the end group modification reaction is finished, the invention preferably further comprises purifying the obtained end group modification reaction solution, wherein the purification method is solvent precipitation purification; the separation and purification are carried out according to the solubility of the polymer in different solvents. In the embodiment of the invention, the solvent precipitation purification reagent is preferably deionized water; the purification process preferably comprises: and mixing the obtained end group modification reaction liquid with water, washing and drying the obtained precipitate to obtain the epoxy end group fluorine-containing hyperbranched structure interface compatilizer. In the invention, the volume ratio of the water to the end group modification reaction solution is (4-10): 1. in the invention, the washing time is preferably 3 times, the drying is preferably carried out in an oven, and the drying temperature is preferably 40-60 ℃, and more preferably 50 ℃; the time is preferably 12-24 h, and more preferably 12 h.
The invention also provides a wave-transparent composite material which comprises the following components in parts by weight:
40-60 parts of PBO fiber, 0.28-0.38 part of interfacial compatilizer and 39.72-59.62 parts of cyanate ester resin; the interface compatilizer is the epoxy end group fluorine-containing hyperbranched structure interface compatilizer in the technical scheme or the epoxy end group fluorine-containing hyperbranched structure interface compatilizer obtained by the preparation method in the technical scheme.
The wave-transparent composite material provided by the invention comprises 20-60 parts by weight of PBO fiber, preferably 50-60 parts by weight, and further preferably 55 parts by weight; the diameter of the PBO fiber is preferably 8-12 μm. In the present invention, the PBO fibers are preferably PBO fibers purchased from shanghai remyand wary limited.
Based on the weight parts of the PBO fibers, the wave-transmitting composite material provided by the invention comprises 39.72-59.62 parts of cyanate ester resin, preferably 39.72-49.65 parts, further preferably 44-45 parts, and more preferably 44.68 parts; the cyanate ester resin is preferably bisphenol A cyanate ester resin (BADCy); the bisphenol A cyanate ester resin is preferably a bisphenol A cyanate ester resin purchased from Jiangsu Wuqiao resin factory.
Based on the weight parts of the PBO fibers, the wave-transmitting composite material provided by the invention comprises 0.28-0.38 parts of interface compatilizer, preferably 0.32-0.37 parts, and further preferably 0.32 parts; the interface compatilizer is the epoxy end group fluorine-containing hyperbranched structure interface compatilizer in the technical scheme or the epoxy end group fluorine-containing hyperbranched structure interface compatilizer obtained by the preparation method in the technical scheme.
In the invention, the epoxy end group fluorine-containing hyperbranched structure interface compatilizer is used as a novel interface compatilizer molecule, and the fluorine-containing group and the hyperbranched topological structure in the molecular structure can improve the dielectric property of the cyanate ester resin; the PBO-like structure can improve the interface compatibility between the matrix and the fiber; in addition, the epoxy end group fluorine-containing hyperbranched structure interface compatilizer has a special hyperbranched topological structure, and the terminal epoxy group can generate copolymerization reaction with cyanate ester resin, so that the mechanical property of the epoxy end group fluorine-containing hyperbranched structure interface compatilizer can be obviously improved. Therefore, the introduction of the epoxy-terminated fluorine-containing hyperbranched structure interface compatilizer into the PBO fiber/cyanate ester resin laminated wave-transparent composite material is expected to synchronously improve the dielectric property, the mechanical property and the insulating property of the final laminated wave-transparent composite material.
The invention also provides a preparation method of the wave-transparent composite material in the technical scheme, which comprises the following steps:
mixing the interfacial compatilizer and a second organic solvent, and then mixing the mixture with cyanate ester resin for prepolymerization to obtain a prepolymer;
sequentially mixing the prepolymer with a third organic solvent and di-n-butyltin dilaurate to obtain a prepreg;
and mixing the prepreg and the PBO fiber, and performing mould pressing and curing after the third organic solvent is volatilized to obtain the wave-transparent composite material.
The interfacial compatilizer and the second organic solvent are mixed and then mixed with the cyanate ester resin for prepolymerization to obtain the prepolymer.
In the present invention, the second organic solvent is preferably N, N-dimethylformamide or N, N-dimethylacetamide, and more preferably N, N-dimethylformamide; the mass ratio of the interfacial compatilizer to the second organic solvent is preferably (0.28-0.38): 1, more preferably (0.32 to 0.37): 1, more preferably 0.32: 1.
in the invention, the prepolymerization temperature is preferably 120-150 ℃, more preferably 140-150 ℃, and more preferably 150 ℃; the time is preferably 15 to 25min, more preferably 20 to 25min, and still more preferably 20 min.
In the invention, the prepolymerization is carried out at 130-150 ℃, so the second organic solvent can volatilize; meanwhile, the prepolymerization reaction occurs because the prepolymerization temperature reaches the lower prepolymerization temperature limit of the resin, but the prepolymerization degree of the resin is low because the prepolymerization temperature is low and the prepolymerization time is short, and most of the obtained prepolymer still exists in the form of a mixture of an interfacial compatilizer and a cyanate resin.
In the present invention, after the pre-polymerization, the pre-polymerization system is preferably subjected to a defoaming treatment, the defoaming treatment is preferably performed in an oven, and the setting of the drying parameters in the present invention is not particularly limited as long as the defoaming is complete.
After the prepolymer is obtained, the prepolymer is sequentially mixed with a third organic solvent and di-n-butyltin dilaurate to obtain the pre-dipped glue.
In the present invention, the third organic solvent is preferably acetone; the volume ratio of the prepolymer to the third organic solvent is preferably (0.8-1.2): (0.9 to 1.1), and more preferably 1: 1; the volume of the di-n-butyltin dilaurate is preferably 0.4 to 0.6%, and more preferably 0.5% of that of the cyanate ester resin.
After the prepreg is obtained, the prepreg and the PBO fiber are mixed, and after a third organic solvent is volatilized, the wave-transmitting composite material is obtained through mould pressing and curing.
In the invention, the pressure of the mould pressing solidification is preferably 5-10 MPa, and more preferably 10 MPa; the mold pressing curing preferably comprises a first curing, a second curing, a third curing and a fourth curing which are sequentially carried out; the first curing temperature is preferably 140-160 ℃, further preferably 150 ℃, and the time is preferably 1 h; the second curing temperature is preferably 170-180 ℃, preferably 180 ℃, and the time is preferably 2 h; the third curing temperature is preferably 190-210 ℃, preferably 200 ℃, the time is preferably 5-6 h, the fourth curing temperature is preferably 220-230 ℃, further preferably 220 ℃, and the time is preferably 2 h. In the present invention, the rate of raising the temperature from room temperature to the temperature of the first curing, the rate of raising the temperature from the temperature of the first curing to the temperature of the second curing, the rate of raising the temperature from the temperature of the second curing to the temperature of the third curing, and the rate of raising the temperature from the temperature of the third curing to the temperature of the fourth curing are independently preferably 5 ℃/min.
The following examples are provided to describe the epoxy-terminated fluorine-containing hyperbranched structure interface compatibilizer, the preparation method thereof, the wave-transparent composite material, and the preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.
The PBO fibers used in the following examples are preferably PBO fibers available from the Shanghai Ruyan waramax corporation; the bisphenol A cyanate ester resin is the bisphenol A cyanate ester resin purchased from Jiangsu Wuqiao resin factory.
Example 1
Under argon, 0.75 parts by weight of t-butyldimethylchlorosilane, 0.36 parts by weight of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 0.5 parts by weight of triethylamine were added to a round-bottom flask, and then 6 parts by weight of N-methylpyrrolidone was added thereto and stirred uniformly. And introducing argon into the mixed solution for 40min, and sealing the reaction system. Then, the round bottom flask was put into a constant temperature oil bath at 25 ℃ and the reaction was continued for 24 hours. Then, 0.27 part by weight of trimesoyl chloride was dissolved in 6 parts by weight of N-methylpyrrolidone, and the solution was dropped (dropping rate was 60 drops/min) into the reaction system under argon and ice bath conditions, followed by further reaction for 24 hours. Then 0.2 weight part of triethylamine is added into the reaction system, after stirring for 3h at 1200r/min, 0.2 weight part of Glycidol (GI) is added continuously, and the reaction is continued for 24h at 25 ℃. And finally pouring the reacted solution into a large amount of deionized water, repeatedly washing for 3 times after polymer is separated out, and drying in a 50 ℃ oven for 12 hours to obtain the epoxy end group fluorine-containing hyperbranched structure interface compatilizer.
According to ISO 1628-1: 1998, the intrinsic viscosity coefficient of the obtained epoxy-terminated fluorine-containing hyperbranched structure interface compatilizer at 25 ℃ is tested by using an Ubbelohde viscometer (the testing solvent is N-methyl pyrrolidone), and the result is that: 0.168 g/dL.
FIG. 1 shows that epoxy end group fluorine-containing hyperbranched structure interface compatilizer1H NMR spectrum, as can be seen from fig. 1: the peaks at 0.05ppm and 0.85ppm of chemical shift can be assigned to the-CH directly linked to Si in the tert-butyldimethylsilyl chloride (TBS) structure, respectively3and-C (CH)3) -a hydrogen atom on; peaks at 7.02ppm and 10.01ppm can be assigned to the carbon atom adjacent to the hydroxyl group on the benzene ring in the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) structure and the hydrogen atom on the imino group in the amide group, respectively; peaks at 7.87ppm and 8.66ppm were assigned to the hydrogen atom on the benzene ring adjacent to the hexafluoropropyl and imino groups in the 6FAP structure and the hydrogen atom on the benzene ring in the trimesoyl chloride (TMC) structure, respectively. In addition, fine peaks appearing at 2-4 ppm in the spectrogram belong to hydrogen atoms in the epoxy terminal groups, which indicates that the terminal group modification reaction is successfully carried out. Meanwhile, the ratio of each peak area in the spectrogram is a: b: c: d: e: f is 5.98: 9.72: 2.11:1.26: 1.82: 1.00, the number ratio of hydrogen atoms in the expected structure is basically consistent, which indicates the successful synthesis of the epoxy end group fluorine-containing hyperbranched structure interface compatilizer of the target product.
FIG. 2 shows the epoxy-terminated fluorine-containing hyperbranched structure interface compatilizer13C NMR spectrum, FIG. 3 is an enlarged view within the circular dashed box of FIG. 2; as can be seen from fig. 2 and 3: the appearance of three peaks in chemical shift values of-2.76 ppm, 18.24ppm and 26.25ppm proves that the TBS structure is successfully accessed into the epoxy end group fluorine-containing hyperbranched structure interface compatilizer; the 166.57ppm peak was attributed to the carbonyl group formed by the condensation reaction between the 6FAP monomer and TMC monomer, demonstrating the successful progress of the polycondensation reaction; the 63.12ppm and 116.31ppm peaks are assigned to the-CF and hexafluoropropyl groups in the 6FAP structure, respectively3To carbon atoms and-CF3To the carbon atom directly attached to the F atom; and 47.26ppm, 64.43pThe appearance of three peaks in pm and 71.13ppm demonstrated successful grafting of the terminal epoxy groups to the hyperbranched fluorochemical interfacial compatibilizer.
FIG. 4 is a FT-IR spectrum of the epoxy-terminated fluorine-containing hyperbranched structure interfacial compatilizer, and it can be seen from FIG. 4 that: compared with 6FAP, the epoxy end group fluorine-containing hyperbranched structure interface compatilizer is 3000cm-1The strong association peak of the hydroxyl and the amino on the left and the right is obviously weakened and 1660cm-1And 980cm-1The strong absorption peak of carbonyl and the absorption peak of epoxy end group are respectively shown, which proves the successful preparation of the epoxy end group fluorine-containing hyperbranched structure interface compatilizer.
Dissolving 0.32 part by weight of epoxy end group fluorine-containing hyperbranched structure interface compatilizer in 1 part by weight of N, N-dimethylformamide to prepare an epoxy end group fluorine-containing hyperbranched structure interface compatilizer solution, then adding the epoxy end group fluorine-containing hyperbranched structure interface compatilizer solution into 44.68 parts by weight of bisphenol A type cyanate resin, uniformly mixing at 150 ℃ to remove the solvent (N, N-dimethylformamide) and prepolymerizing to a gel point to obtain a prepolymer; cooling the prepolymer to room temperature, and then mixing the prepolymer and acetone according to the volume ratio of 1:1, adding acetone and mixing the cyanate ester resin and the di-n-butyltin dilaurate according to the volume ratio of 100: 0.5 adding di-n-butyltin dilaurate to prepare a prepreg; and compounding the obtained prepreg with 55 parts by weight of PBO fibers, performing compression molding under the pressure of 10MPa after acetone is volatilized, and curing according to the program of 150 ℃/1h +180 ℃/2h +200 ℃/5h +220 ℃/2h, wherein the heating rate is 5 ℃/min, so as to prepare the wave-transparent composite material.
Example 2
Under argon, 0.77 parts by weight of t-butyldimethylchlorosilane, 0.35 parts by weight of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 0.6 parts by weight of triethylamine were added to a round-bottom flask, and then 5 parts by weight of N-methylpyrrolidone was added thereto and stirred uniformly. And introducing argon into the mixed solution for 40min, and sealing the reaction system. Then, the round bottom flask was put into a constant temperature oil bath at 25 ℃ and the reaction was continued for 24 hours. Then, 0.27 part by weight of trimesoyl chloride was dissolved in 7 parts by weight of N-methylpyrrolidone, and the solution was added dropwise (dropwise addition rate was 50 drops/min) to the reaction system under argon and ice bath conditions, followed by further reaction for 24 hours. Then 0.3 weight part of triethylamine is added into the reaction system, 0.2 weight part of Glycidol (GI) is added after stirring for 3h at 1000r/min, and the reaction is continued for 24h at 25 ℃. And finally pouring the reacted solution into a large amount of deionized water, repeatedly washing for 3 times after polymer is separated out, and drying in a 50 ℃ oven for 14 hours to obtain the epoxy end group fluorine-containing hyperbranched structure interface compatilizer.
According to ISO 1628-1: 1998, the intrinsic viscosity coefficient of the obtained epoxy-terminated fluorine-containing hyperbranched structure interface compatilizer at 25 ℃ is tested by using an Ubbelohde viscometer (the testing solvent is N-methyl pyrrolidone), and the result is that: 0.165 g/dL.
Dissolving 0.35 part by weight of epoxy end group fluorine-containing hyperbranched structure interface compatilizer in 1 part by weight of N, N-dimethylformamide to prepare an epoxy end group fluorine-containing hyperbranched structure interface compatilizer solution, then adding the epoxy end group fluorine-containing hyperbranched structure interface compatilizer solution into 44.65 parts by weight of bisphenol A type cyanate resin, uniformly mixing at 150 ℃ to remove the solvent, and carrying out prepolymerization to gel point to obtain a prepolymer; cooling the prepolymer to room temperature, and then mixing the prepolymer and acetone according to the volume ratio of 1:1, adding acetone and mixing the cyanate ester resin and the di-n-butyltin dilaurate according to a volume ratio of 100: 0.5 dropwise adding di-n-butyltin dilaurate to prepare a prepreg; and compounding the obtained prepreg with 55 parts by weight of PBO fibers, performing compression molding under the pressure of 10MPa after acetone is volatilized, and curing at the curing process of 150 ℃/1h +180 ℃/2h +200 ℃/5h +220 ℃/2h, wherein the heating rate is 5 ℃/min, so as to obtain the wave-transparent composite material.
Example 3
Under argon, 0.76 part by weight of t-butyldimethylchlorosilane, 0.35 part by weight of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 0.6 part by weight of triethylamine were charged into a round-bottomed flask, and then 5 parts by weight of N-methylpyrrolidone was added thereto and stirred uniformly. And introducing argon into the mixed solution for 40min, and sealing the reaction system. Then, the round bottom flask was put into a constant temperature oil bath at 25 ℃ and the reaction was continued for 22 h. Then, 0.27 part by weight of trimesoyl chloride was dissolved in 7 parts by weight of N-methylpyrrolidone, and the solution was added dropwise (at a dropping rate of 35 drops/min) to the reaction system under argon and ice bath conditions, followed by further reaction for 26 hours. Then 0.3 weight part of triethylamine is added into the reaction system, 0.2 weight part of Glycidol (GI) is added after stirring for 1h at the speed of 800r/min, and the reaction is continued for 20h at the temperature of 25 ℃. And finally pouring the reacted solution into a large amount of deionized water, repeatedly washing for 3 times after polymer is separated out, and drying in a 50 ℃ oven for 14 hours to obtain the epoxy end group fluorine-containing hyperbranched structure interface compatilizer.
According to ISO 1628-1: 1998, the intrinsic viscosity coefficient of the obtained epoxy-terminated fluorine-containing hyperbranched structure interface compatilizer at 25 ℃ is tested by using an Ubbelohde viscometer (the testing solvent is N-methyl pyrrolidone), and the result is that: 0.162 g/dL.
Dissolving 0.37 parts by weight of epoxy end group fluorine-containing hyperbranched structure interface compatilizer in 1 part by weight of N, N-dimethylformamide to prepare an epoxy end group fluorine-containing hyperbranched structure interface compatilizer solution, then adding the epoxy end group fluorine-containing hyperbranched structure interface compatilizer solution into 44.63 parts by weight of bisphenol A type cyanate ester resin, uniformly mixing at 150 ℃ to remove a solvent and prepolymerizing to a gel point to obtain a prepolymer, cooling the prepolymer to room temperature, adding acetone according to a volume ratio of the prepolymer to the acetone of 1:1, and adding 100 parts by volume of cyanate ester resin to di-N-butyltin dilaurate: 0.5 adding di-n-butyltin dilaurate to prepare a prepreg; and compounding the obtained prepreg with 55 parts by weight of PBO fibers, performing compression molding under the pressure of 10MPa after acetone is volatilized, and curing at the curing process of 150 ℃/1h +180 ℃/2h +200 ℃/5h +220 ℃/2h, wherein the heating rate is 5 ℃/min, so as to obtain the wave-transparent composite material.
Comparative example 1
Prepolymerizing 45 parts by weight of bisphenol A type cyanate ester resin at 150 ℃ to gel point, cooling to room temperature, and then mixing the prepolymer and acetone according to a volume ratio of 1:1, adding acetone, and mixing the cyanate ester resin and the di-n-butyltin dilaurate according to the volume ratio of 100: 0.5 adding di-n-butyltin dilaurate to prepare a prepreg; and compounding the obtained prepreg with 55 parts by weight of PBO fibers, carrying out compression molding under the pressure of 10MPa after acetone is volatilized, and curing according to the curing process of 150 ℃/1h +180 ℃/2h +200 ℃/5h +220 ℃/2h to obtain the wave-transparent composite material.
The properties of the wave-transparent composite materials obtained in examples 1 to 3 and comparative example 1 were measured, and the results are shown in table 1.
TABLE 1 Properties of wave-transparent composites obtained in examples 1-3 and comparative example 1
As can be seen from table 1: the wave-transparent composite material is prepared by adopting the epoxy end group fluorine-containing hyperbranched structure interface compatilizer, so that the dielectric property and the mechanical property of the wave-transparent composite material and the interface compatibility between a matrix and fibers are effectively improved. When the addition amount of the epoxy end group fluorine-containing hyperbranched structure interface compatilizer is 7 wt% of the mass of the cyanate ester resin (corresponding to example 1), the obtained wave-transparent composite material has the best dielectric property, the epsilon and the tan delta of the wave-transparent composite material under 1MHz are respectively 2.65 and 0.003, the epsilon and the tan delta of the wave-transparent composite material are respectively 3.04 and 0.0059, the dielectric property is improved by 12.8% and 49.1% compared with the wave-transparent composite material obtained by comparative example 1, the mechanical property is excellent (the bending strength and the interlaminar shear strength (ILSS) are respectively 634.9MPa and 46.9MPa), and the corresponding volume resistivity and the breakdown voltage are respectively 4.93 multiplied by 1015Omega cm and 25.38 kV/mm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An epoxy end group fluorine-containing hyperbranched structure interface compatilizer is characterized by having a structure shown in a formula I:
in the formula I, m and n are positive integers; the interfacial compatilizer with the epoxy end group fluorine-containing hyperbranched structure has an intrinsic viscosity coefficient of 0.160-0.168 g/dL at 25 ℃.
2. The preparation method of the epoxy end group fluorine-containing hyperbranched structure interface compatilizer of claim 1, which is characterized by comprising the following steps:
mixing tert-butyldimethylchlorosilane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, first triethylamine and a first organic solvent, and carrying out a silyl group protection reaction to obtain a silyl group protection reaction solution;
dropwise adding trimesoyl chloride into the silane-based protective reaction liquid to carry out polycondensation reaction to obtain polycondensation reaction liquid;
and mixing the polycondensation reaction liquid with second triethylamine and glycidol in sequence, and carrying out end group modification reaction to obtain the epoxy end group fluorine-containing hyperbranched structure interface compatilizer.
3. The production method according to claim 2, wherein the mass ratio of the tert-butyldimethylsilyl chloride, the 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, the first triethylamine and the first organic solvent is (0.7 to 0.8): (0.34-0.38): (0.46-0.6): (4-6); the silane-based protection reaction is carried out under the atmosphere of argon; the temperature of the silane group protection reaction is 15-35 ℃, and the time is 20-28 h.
4. The method according to claim 2, wherein the mass ratio of trimesoyl chloride to 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is (0.262 to 0.268): (0.34-0.38); the polycondensation reaction is carried out under the condition of ice-water bath; the time of the polycondensation reaction is 24 hours.
5. The production method according to claim 2, wherein the mass ratio of the second triethylamine, glycidol, and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is (0.15 to 0.3): (0.1-0.2): (0.34-0.38); the temperature of the end group modification reaction is room temperature, and the time is 20-28 h.
6. The wave-transparent composite material is characterized by comprising the following components in parts by weight:
40-60 parts of PBO fiber, 0.28-0.38 part of interfacial compatilizer and 39.72-59.62 parts of cyanate ester resin;
the interfacial compatilizer is the epoxy end group fluorine-containing hyperbranched structure interfacial compatilizer disclosed in claim 1 or the epoxy end group fluorine-containing hyperbranched structure interfacial compatilizer prepared by the preparation method disclosed in any one of claims 2-5.
7. The method of preparing the wave-transparent composite material of claim 6, comprising the steps of:
mixing the interfacial compatilizer and a second organic solvent, and then mixing the mixture with cyanate ester resin for prepolymerization to obtain a prepolymer;
sequentially mixing the prepolymer with a third organic solvent and di-n-butyltin dilaurate to obtain a prepreg;
and mixing the prepreg and the PBO fiber, and performing mould pressing and curing after the third organic solvent is volatilized to obtain the wave-transparent composite material.
8. The method according to claim 7, wherein the prepolymerization temperature is 120 to 150 ℃ and the time is 15 to 25 min.
9. The method according to claim 7, wherein the volume ratio of the prepolymer to the third organic solvent is (0.8-1.2): (0.9 to 1.1); the volume of the di-n-butyltin dilaurate is 0.4-0.6% of that of the cyanate ester resin.
10. The preparation method according to claim 7, wherein the pressure of the mold pressing curing is 5-10 MPa, and the mold pressing curing comprises a first curing, a second curing, a third curing and a fourth curing which are sequentially carried out; the temperature of the first curing is 140-160 ℃, the time is 1h, the temperature of the second curing is 170-180 ℃, the time is 2h, the temperature of the third curing is 190-210 ℃, the time is 5-6 h, and the temperature of the fourth curing is 220-230 ℃, and the time is 2 h.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108384234A (en) * | 2018-03-29 | 2018-08-10 | 西北工业大学 | A kind of wave-penetrating composite material and preparation method thereof |
CN109694478A (en) * | 2018-12-28 | 2019-04-30 | 上海华谊树脂有限公司 | A kind of ultrabranching polyamide and its preparation method and application |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN109694478A (en) * | 2018-12-28 | 2019-04-30 | 上海华谊树脂有限公司 | A kind of ultrabranching polyamide and its preparation method and application |
Non-Patent Citations (2)
Title |
---|
SARAVANAN SUBRAMANIAN ET AL.: "《Sustainable Nanoporous Benzoxazole Networks as Metal-Free Catalysts for One-Pot Oxidative Self-Coupling of Amines by Air Oxygen》", 《ADVANCED SUSTAINABLE SYSTEMS》 * |
ZHENG LIU ET AL.: ""Improved wave-transparent performances and enhanced mechanical properties for fluoride-containing PBO precursor modified cyanate ester resins and their PBO fibers/cyanate ester composites"", 《COMPOSITES PART B-ENGINEERING》 * |
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