CN101402729B - Cyanate resin composition and method of producing the same - Google Patents
Cyanate resin composition and method of producing the same Download PDFInfo
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- CN101402729B CN101402729B CN2008102266324A CN200810226632A CN101402729B CN 101402729 B CN101402729 B CN 101402729B CN 2008102266324 A CN2008102266324 A CN 2008102266324A CN 200810226632 A CN200810226632 A CN 200810226632A CN 101402729 B CN101402729 B CN 101402729B
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Abstract
The invention discloses a cyanic acid ester resin composition and a preparation method thereof. The cyanic acid ester resin composition provided by the invention comprises a modifier and a tetramethyl bisphenol F-typed cyanic acid ester preformed polymer, wherein, the modifier comprises bisphenol E-typed cyanic acid ester. The electrical property and the heat resistance property of modified cyanic acid ester resin composition are very superior and the modified cyanic acid ester resin composition is liquid at normal temperature, thus being capable of being applied to winding or RTM forming technology and having excellent manufacturability.
Description
Technical field
The present invention relates to a kind of cyanate resin composition and preparation method thereof, and the goods of making by this cyanate resin composition.
Background technology
Resin plays binding agent in matrix material, be the stable on heating basal component of decision matrix material.Thermosetting resins such as traditional resin matrix such as unsaturated polyester resin, Resins, epoxy, resol still are widely used in various radomes, and in addition silicone resin polyimide novel fire resistant resins such as (PI) also begins to come into operation gradually.Thermoplastic resin is shown up prominently in the preparation of radome in recent years, and wherein the most noticeable is the noncharring ablator polytetrafluoroethylene PTFE of U.S.'s development.
Cyanate ester resin is applied aspect radome after entering the eighties in 20th century gradually.Its principal feature is: low dielectric coefficient (2.8～3.2), minimum tangent of the dielectric loss angle value (0.002～0.008), and the temperature-160～(Tg-50) of broadness ℃, range of frequency (106～1011Hz) change very little; High heat resistance (Tg:240～290 ℃), instantaneous thermotolerance (heat decomposition temperature) is far above Resins, epoxy; Low rate of moisture absorption (＜1.5%); Little coefficient of thermal expansion; Excellent mechanical property and adhesiveproperties; Have the manufacturability similar, dissolve in the usual vehicle to Resins, epoxy, easily and strongthener compound, no low-molecular material is separated out in the solidification process, can be in 177 ℃ of curing.
Cyanate ester resin is the new type resin that a class has excellent properties, compare with present a large amount of EP, BMI that use and resol etc., have many outstanding advantages, its dielectric properties are far superior to EP and BMI, in very wide temperature range (160 ℃～220 ℃) and range of frequency (10
4～10
11Hz) have stable and extremely low specific inductivity ((2.8～3.2) and dielectric loss (0.002～0.006) in; Thermotolerance is lower than BMI and is higher than EP, and at high temperature has better stability, and hydrothermal stability is better than EP and BMI; Water-absorbent is better than EP and BMI; Mechanical property and EP and BMI are suitable or the like.Also have good flame, low being fuming and performance such as anti-ablation simultaneously, it is performance resins based composites ideal body material, have a wide range of applications in many fields such as aerospace, automobile, electronics, military projects, particularly involve thoroughly in high-speed figure and high frequency printed circuit board, high-performance and have huge application potential aspect stealth material and the aerospace load bearing structure material, its development prospect is noticeable.
Complete purified cyanate resin alicyclic monomer is that curing reaction does not take place under heating condition.Cyanate ester resin (Cyanate Ester Resin, CE) do not adding under the condition of any catalyzer, a critical condition that influences ethylene rhodanate resin curing is must have---intermediate product---iminocarbonic acid dibasic acid esters in the system, it is in the ethylene rhodanate resin curing reaction process, is formed by cyanate resin alicyclic monomer and the reaction of impurity phenolic hydroxyl group.During curing, must contain a spot of impurity (as water, phenol) in the system and cause curing reaction.Bauer et al. thinks that the reaction of second step is that iminocarbonic acid dibasic acid esters and two OCN radical reactions generate triazine ring, and the regenerated phenolic hydroxyl group can be recycled, constantly increase until the cyanate ester resin molecular weight, obtain a kind of triazine (Triazine) that contains at last and encircle cancellated polymkeric substance.Its polymerization reaction mechanism is shown below:
This kind structure is given the dielectric properties of its excellence just, higher second-order transition temperature, and this polymkeric substance also has low-shrinkage simultaneously, excellent mechanical property and adhesive property etc., complete processing is near Resins, epoxy.
The kind of cyanate ester resin is more, Ciba in the world, and Lonza, companies such as Dow are all producing the different structure cyanate, and the cyanate ester monomer of main several structures is shown in Table 1 at present, and the dielectric properties of resin are very superior.
Several cyanate ester monomers of table 1
Cyanate ester resin is with its superior complete processing and the advantage good with other resin blending, and the cyanate ester resin over-all properties comes out at the top in numerous performance resinss.At present, the resin matrix that is adapted to the submarine antenna cover material is the most suitable with the cyanate ester resin of dicyclopentadiene bisphenol type, tetramethyl-Bisphenol F type and three kinds of structures of bis-phenol M type, because the water-intake rate of these three kinds of resins is minimum, electrical property is superior, do not produce but bis-phenol M type resin is at present domestic, and very expensive.Though the electrical property of bisphenol E-type resin is not as other structural resin electrical property, the bisphenol E-type resin is to be liquid cyanate ester resin under unique a kind of normal temperature, and price is also relatively more expensive naturally.Dicyclopentadiene bisphenol type cyanate ester resin is with the oligomer of inert solvent butanone dilution, can be applied to winding shaping process, but the voidage of moulding product is higher.
Successful synthetic cyanate ester resin is except that bisphenol E-type is low-viscosity (mobile) liquid, most cyanate ester monomers are crystalline solid, can not be applied to the composite material process planning (moulding processs such as for example wet method is Wrapping formed, VA RTM) of formed at normal temp, the application of cyanate ester resin is most by making prepreg, is applied to converted products again.
Summary of the invention
The purpose of this invention is to provide and be liquid cyanate resin composition and preparation method thereof under a kind of normal temperature.
Cyanate resin composition provided by the present invention comprises properties-correcting agent and with auto-polymerization mode polymeric tetramethyl-Bisphenol F type cyanate performed polymer, wherein, described properties-correcting agent comprises bisphenol E-type cyanate.
In one embodiment, the refractive index of tetramethyl-Bisphenol F type cyanate performed polymer is 1.576～1.582.Perhaps, in another embodiment, the transformation efficiency of cyano group is 32～38% in the tetramethyl-Bisphenol F type cyanate performed polymer.
In one embodiment, the weight ratio of properties-correcting agent and described tetramethyl-Bisphenol F type cyanate performed polymer is 1: 2～1: 1.Perhaps, in another embodiment, properties-correcting agent is 30～50 weight % of described composition.
The method for preparing cyanate resin composition provided by the present invention comprises:
A) provide tetramethyl-Bisphenol F type cyanate performed polymer;
B) with properties-correcting agent and the combination of described tetramethyl-Bisphenol F type cyanate performed polymer;
Wherein, described properties-correcting agent comprises bisphenol E-type cyanate.
In one embodiment, step a) is carried out in following condition: make tetramethyl-Bisphenol F type cyanate carry out polymerization, tetramethyl-Bisphenol F type cyanate performed polymer is provided.Preferably, the polymeric temperature is 190～220 ℃.
In one embodiment, the refractive index of tetramethyl-Bisphenol F type cyanate performed polymer is 1.576～1.582; Perhaps, the transformation efficiency of cyano group is 32～38% in the described tetramethyl-Bisphenol F type cyanate performed polymer.
In one embodiment, the weight ratio of properties-correcting agent and described tetramethyl-Bisphenol F type cyanate performed polymer is 1:2～1:1.
The present invention also comprises the goods of being made by above-mentioned cyanate resin composition.
The application is by carrying out study on the modification to tetramethyl-Bisphenol F type cyanate ester resin, the making of having finished cyanate ester resin prepolymer of success, improved the manufacturability of cyanate ester resin, obtained superior performance can be used for twine or the Cyanate Ester Resin Modified of RTM moulding process, main innovate point is as follows:
Curing reaction mechanism by cyanate ester resin and polyreaction thereof be to the dependent research of temperature-time, and determined reasonable feasible cyanate ester resin prepolymer manufacture craft through overtesting;
Relation by research tetramethyl-Bisphenol F type cyanate performed polymer cyano group transformation efficiency and resin prepolymer refractive index, reach crystallization time appears in the resin prepolymer refractive index with it discussion, determined rational controlling index---the refractive index of working life than long tetramethyl-Bisphenol F type cyanate performed polymer manufacture craft;
Obtained a kind of modified cyanic acid ester resin composition of excellent performance, the electrical property of modified cyanic acid ester resin and resistance toheat are very superior, and normal temperature can be applied to twine or the RTM moulding process, and manufacturability is good down for liquid simultaneously.
Description of drawings
Fig. 1 is a tetramethyl-Bisphenol F type cyanate heating and melting curve.
Fig. 2 A～2D is the DSC experimental test curve of tetramethyl-Bisphenol F type cyanate ester resin under the different heat-up rates, and wherein the heat-up rate of Fig. 2 A～2D is respectively 2 ℃/min, 5 ℃/min, 10 ℃/min, 20 ℃/min.
Fig. 3 is the curing process parameter analysis.
Fig. 4 A and 4B are respectively the ln β/TP2-1/TP linear regression of first peak temperature and second peak temperature.
Fig. 5 A～5F illustrates tetramethyl-Bisphenol F type cyanate ester resin constant temperature DSC experimental test result, and wherein Fig. 5 A～5F is respectively 150 ℃, 160 ℃, 170 ℃, 180 ℃, 200 ℃ and 230 ℃ of constant difference heating curves.
Fig. 6 is the relation between first exothermic peak concluding time of tetramethyl-Bisphenol F type cyanate ester resin and the temperature of reaction.
Fig. 7 is the infrared absorption spectra of tetramethyl-Bisphenol F type cyanate ester resin.
Fig. 8 A-Fig. 8 E is respectively the infrared absorption spectra of different polymerization degree (refractive index) tetramethyl-Bisphenol F type cyanate ester resin prepolymer: refractive index is respectively 1.572,1.5735,1.5775,1.582,1.589.
Fig. 9 illustrates the curve of the refraction coefficient of resin to the differential responses temperature and time, and polynomial expression is the theoretical fitting curve among the figure, and it has provided refraction coefficient and the Changing Pattern of temperature of reaction and time in the cyanate ester resin prepolymerization reaction process.
Figure 10 shows the relation that occurs crystallization time and refractive index under the tetramethyl-Bisphenol F type cyanate ester resin prepolymer normal temperature.Broken line is the value of actual test, and smooth curve is the theoretical fitting curve, and its variation tendency has provided the ultimate value of the refractive index when crystallization not occurring.
Figure 11 shows modified cyanic acid ester resin and sticks-the Wen curve.
Figure 12 shows modified cyanic acid ester resin constant temperature viscosity to be changed in time.
Figure 13 shows the Wrapping formed product of quartz/cyanate.
Figure 14, Figure 15 are respectively the modified cyanic acid ester resin infrared absorption spectra of 250 ℃/3h and 280 ℃/3h after fixing.
Figure 16 shows modified cyanic acid ester resin specific inductivity and frequency relation.
Figure 17 shows modified cyanic acid ester resin dielectric loss and frequency relation.
Embodiment
First aspect present invention provides a kind of cyanate resin composition, comprises properties-correcting agent and tetramethyl-Bisphenol F type cyanate performed polymer, and described properties-correcting agent comprises bisphenol E-type cyanate.
In one embodiment, this comprises that the properties-correcting agent of bisphenol E-type cyanate can contain other type properties-correcting agent that is different from bisphenol E-type cyanate, and condition is the performance that these other type properties-correcting agent do not damage required cyanate resin composition nocuously.In another embodiment, this properties-correcting agent that comprises bisphenol E-type cyanate can be bisphenol E-type cyanate, that is, this cyanate resin composition comprises bisphenol E-type cyanate and tetramethyl-Bisphenol F type cyanate performed polymer.
In this cyanate resin composition, can use properties-correcting agent and tetramethyl-Bisphenol F type cyanate performed polymer with any ratio, condition is to make final cyanate resin composition be liquid at normal temperatures.Preferably, in one embodiment, the weight ratio of properties-correcting agent and tetramethyl-Bisphenol F type cyanate performed polymer is 1:2～1:1.Perhaps, in another embodiment, this properties-correcting agent is 30～50 weight % of described composition.
As another component of this cyanate resin composition, preferably selecting refractive index is 1.576～1.582, and perhaps the transformation efficiency of cyano group is 32～38% tetramethyl-Bisphenol F type cyanate performed polymer.This point will describe in detail below.
A second aspect of the present invention provides the method for preparing cyanate resin composition, comprising:
A) provide tetramethyl-Bisphenol F type cyanate performed polymer;
B) with properties-correcting agent and the combination of described tetramethyl-Bisphenol F type cyanate performed polymer;
Wherein, described properties-correcting agent comprises bisphenol E-type cyanate.
Tetramethyl-Bisphenol F type cyanate is a white crystalline powder, and 105 ℃ of fusing points, molecular weight 306.36, Fig. 1 are its heating and melting curve.The application selects for use the suitable dilution agent that performed polymer is diluted by making tetramethyl-Bisphenol F type cyanate ester resin prepolymer then, improves the technological purpose of tetramethyl-Bisphenol F type cyanate ester resin to reach.
In one embodiment, step a) is carried out in following condition: make tetramethyl-Bisphenol F type cyanate carry out polymerization, tetramethyl-Bisphenol F type cyanate performed polymer is provided.
Tetramethyl-Bisphenol F type cyanate carries out polymerization can various polymerization methodses, preferably adopt the auto-polymerization mode, promptly, polymerization process does not add catalyzer, solvent etc., with the heating of tetramethyl-Bisphenol F type cyanate, carry out polyreaction under certain condition, obtain tetramethyl-Bisphenol F type cyanate performed polymer.
Below will describe the condition of this process in detail.
1. tetramethyl-Bisphenol F type ethylene rhodanate resin curing repercussion study
Measure differential scanning calorimetric (DSC) curve of resin with the Pyris-1 type thermal analyzer of PE company.Test condition: temperature rise rate is respectively 2 ℃/min, 5 ℃/min, 10 ℃/min, the heating curve of 20 ℃/min, 120 ℃～380 ℃ of temperature ranges.
The DSC experimental test result of tetramethyl-Bisphenol F type cyanate ester resin is shown in Fig. 2 A～2D.Be easy to from figure find out that there are two exothermic peaks in the solidification process of resin, first exothermic peak is more remarkable when temperature rise rate is smaller, and temperature rise rate when higher second exothermic peak more remarkable.Fig. 2 A～2D response feature parametric statistics sees Table 2.
Table 2 differential thermal analysis DSC parametric statistics table
According to DSC experimental test result, adopt extrapotation to calculate curing process parameter, result such as Fig. 3.
When Fig. 3 can clearly obtain temperature rise rate and is 0 ℃/min, the beginning temperature of reaction of tetramethyl-Bisphenol F type cyanate ester resin, first, second exothermic peak temperature and reaction end temp were respectively 166.5 ℃, 219.52 ℃, 245.13 ℃ and 307.46 ℃.
With reference to homothermic DSC curve, again according to gel test correction curing process parameter.
No matter in the cyanate ester resin system catalyst-free is arranged, all available simple formula of its curing reaction Kinetics rate process is described.Simon and Gilham have proposed second order reaction kinetic model a: da/dt=k
1(1-a)
2+ k
2A (1-a); Wherein a is the transformation efficiency of cyano group.
Use this equation, can describe the whole curing reaction course of cyanate ester resin preferably.When curing reaction temperature or catalyst concn were enough high, the initial stage of curing reaction can be ignored, and then reaction meets n level kinetic equation a: da/dt=k (1-a) n.For tetramethyl-Bisphenol F type cyanate ester resin system, no matter catalyst-free is arranged, its curing reaction meets first _ order kinetics equation: da/dt=k (1-a).
By the Kissinger equation:
In the formula: β---temperature rise rate;
T
P---peak temperature;
E---reaction activity;
A---frequency factor.
Record the peak temperature T of different temperature rise rates (β) above reaching
P, right
Make linear regression such as Fig. 4 A and 4B, try to achieve activation energy of curing reaction E and frequency factor lnA by the collinear slope.
Table 3 tetramethyl-Bisphenol F type cyanate ester resin DSC first peak Value Data is analyzed
The table 4 tetramethyl-Bisphenol F type cyanate ester resin DSC second peak-data analysis
By one-variable linear regression equation y=a+bx, can win peak value a=6.3371, b=-10853, the second peak value a=8.7772, b=-13761.Bring the Kissinger equation into, get the curing reaction first activation energy E=90.23kJ of tetramethyl-Bisphenol F type cyanate ester resin, frequency factor lnA=15.63sec
-1The second activation energy E=114.41kJ, frequency factor lnA=18.31sec
-1
2. temperature and time is to the influence of tetramethyl-Bisphenol F type cyanate polyreaction
Tetramethyl-Bisphenol F type cyanate ester resin constant temperature DSC experimental test result is shown in Fig. 5 A～5F.
Exothermic peak does not appear in 150 ℃ of constant temperature curves shown in Fig. 5 A, illustrates that resin does not have polymerization reaction take place.160 ℃ of constant temperature curves exothermic phenomenon just occurred from beginning 2.8min shown in Fig. 5 B, and when exothermic peak appeared at 111min, the concluding time was 241min.
By Fig. 5 C, 170 ℃ of constant temperature curve exothermic peak scopes are 2.9min～130min, when exothermic peak appears at 38.4min.By Fig. 5 D, 180 ℃ of constant temperature curve exothermic peak scopes are 2.2min～78.6min, when exothermic peak appears at 38.2min.
By Fig. 5 E, the scope that exothermic peak appears in 200 ℃ of constant temperature curves is 0～36min, does not measure the time that exothermic peak occurs.By Fig. 5 F, the time that exothermic peak occurs is not measured in 230 ℃ of constant temperature curve first exothermic peak end when 18min greatly equally, second exothermic peak occurred between 65.6min～138.6min, when peak value appears at 99.85min.Illustrate need the post curing treatment that is higher than 230 ℃ behind this resin solidification just can completion of cure.
Fig. 6 is the relation between first exothermic peak concluding time of tetramethyl-Bisphenol F type cyanate ester resin and the temperature of reaction.
3. tetramethyl-Bisphenol F type cyanate ester resin polyreaction infrared analysis
The infrared absorption spectra of tetramethyl-Bisphenol F type cyanate ester resin as shown in Figure 7,2241cm
-1And 2277cm
-1Be the cyano group charateristic avsorption band.
The different batches tetramethyl-Bisphenol F type cyanate performed polymer that the application has made carries out infrared test, the infrared absorption spectra of different polymerization degree resin prepolymer is shown in Fig. 8 A-8E (refractive index is respectively 1.572,1.5735,1.5775,1.582,1.589), and the triazine ring absorption peak is at 1560cm
-1, 1365cm
-1The place.
The result shows that along with the raising of polyreaction degree, the absorption peak of-OCN group will dwindle, and the absorption peak of triazine ring will strengthen, and at 1134cm
-1The absorption peak of the C-O-ph of place group does not change with the reaction times.Be calculated as follows level of response P:
P=[(E
Cyanogen/ E
Ginseng)
Before the reaction-(E
Cyanogen/ E
Ginseng)
After the reaction]/(E
Cyanogen/ E
Ginseng)
Before the reaction(2.3)
Wherein, E
Cyanogen: the absorbancy of-OCN group; E
Ginseng: the absorbancy of C-O-ph group
E＝1n(I
0/I) (2.4)
I
0: incident intensity; I: transmitted intensity
The application is with 1134cm
-1The absorption peak of the C-O-ph of place group is a reference peak, obtains the transformation efficiency of the tetramethyl-Bisphenol F type cyanate ester resin of different extent of polymerizations.The cyano group transformation efficiency and the refractive index thereof of different batches tetramethyl-Bisphenol F type cyanate performed polymer are shown in Table 5.
The cyano group transformation efficiency of table 5 resin prepolymer
4. the control of tetramethyl-Bisphenol F type cyanate ester resin polyreaction is discussed
The application has carried out the prepolymerization reaction test to tetramethyl-Bisphenol F type cyanate ester resin, and the refraction coefficient of resin in the reaction process is made curve to the differential responses temperature and time, and the result as shown in Figure 9.
Resin refraction coefficient situation over time under the tracing analysis differing temps from figure, refraction coefficient and time curve all flex point occurs at 1.578～1.58 places, slope of a curve reduces in time before the flex point, rate of curve increases sharply in time after the flex point, and expression resin refractive index changes with the cyano group transformation efficiency a milder intermediate stage; Rising slope of a curve with temperature increases, and expression temperature rising resin refractive index increases with the severe degree that the cyano group transformation efficiency changes.
Table 6 is the relations that occur crystalline time and refractive index under the tetramethyl-Bisphenol F type cyanate performed polymer normal temperature.Find through overtesting: tetramethyl-Bisphenol F type cyanate ester resin is transparent amber shape when refractive index is 1.5760-1.5820, can draw haircuts, and is more similar to the state of Resins, epoxy, and the long usage period is arranged.When refractive index is lower than 1.5760, crystallization easily, working life is shorter.When refractive index greater than 1.5820 the time, be hard shape elastomerics under the normal temperature, lose liquid character.
The relation of table 6 crystallization time and refractive index
With refractive index in the table is that 1.584 and 1.592 crystallization time is assumed to be 100 days respectively and 1000 days, and the data in the his-and-hers watches are mapped then, and the result as shown in figure 10.This result shows that refractive index can be stored more than half a year under the tetramethyl-Bisphenol F type cyanate performed polymer normal temperature when 1.5760-1.5820.
According to as can be known above-mentioned, in one embodiment, this provides tetramethyl-Bisphenol F type cyanate performed polymer is to make tetramethyl-Bisphenol F type cyanate at high temperature carry out auto-polymerization, and preferably, the temperature of auto-polymerization is 190～220 ℃.
In order to access the final resin combination that meets the requirements, in one embodiment, making the refractive index of this tetramethyl-Bisphenol F type cyanate performed polymer is 1.576～1.582; Perhaps, in another embodiment, making the transformation efficiency of cyano group in the tetramethyl-Bisphenol F type cyanate performed polymer is 32～38%.
In the step b),, can adopt this area variety of way commonly used, for example mix etc. properties-correcting agent and the combination of described tetramethyl-Bisphenol F type cyanate performed polymer.In one embodiment, the weight ratio of properties-correcting agent and tetramethyl-Bisphenol F type cyanate performed polymer is 1:2～1:1; Perhaps, in another embodiment, this properties-correcting agent is 30～50 weight % of final composition.
In a third aspect of the present invention, the goods that comprise above-mentioned cyanate resin composition are provided.
Because most of cyanate ester resin is a solid at normal temperatures, moulding process is relatively poor, and the application provides modification tetramethyl-Bisphenol F type cyanate ester resin, has not only improved the manufacturability of tetramethyl-Bisphenol F type cyanate, and has obtained excellent performance.Utilize this modification tetramethyl-Bisphenol F type cyanate ester resin can make various matrix materials, also cyanate ester resin can be applied to common winding or RTM moulding process.
Below with specific embodiment the application's all respects are described.
If not explanation in addition, the used various raw materials of following examples all can obtain by commercial sources.
Tetramethyl-Bisphenol F type cyanate ester monomer, white crystalline powder, 105 ℃ of fusing points, molecular weight 306.36, Shanghai Huifeng Technical ﹠ Business Co., Ltd's product.
Properties-correcting agent, bisphenol E-type cyanate
Silica fiber, quartz fabric, silica wool felt etc., Hubei FeiLiHua quartz Glass Co., Ltd's product
Experiment is as follows with equipment and instrument:
Measure differential scanning calorimetry (DSC) curve of blend with the Pyris-1 type thermal analyzer of PE company; Infrared diamond pond ATR spectrogram is by the state of cure of infrared spectra tracking and testing analysis modified cyanic acid ester resin.Temperature-viscosity curve testing tool equipment.Adopt conventional high pressure RTM injection device and sample RTM forming mould.
The preparation of preparation example 1, modified cyanic acid ester resin
Tetramethyl-Bisphenol F type cyanate is added in the four-hole bottle, and (concrete temperature is 200 ℃-220 ℃) carries out the prepolymerization reaction in the oil bath heating environment, with Abbe refractometer control pre-polymerization terminal point; When refractive index is 1.576～1.582, the properties-correcting agent of equivalent is added to waits in the four-hole bottle to stir, promptly obtain modified cyanic acid ester resin.Pour mixed resin into the container cooling, standby.
Sample example 1, specimen preparation
In quartz fabric lay mould, matched moulds, with the modified cyanic acid ester resin preheating that mould and preparation example 1 obtain, vacuum RTM form naturally cools to room temperature after solidifying then, and the demoulding gets goods and sample.
Performance test and data processing:
Measure modified cyanic acid ester resin to stick-test of Wen curve and analysis; Cured article Infrared spectroscopy, soluble part of content measuring, the curing reaction degree of analysis resin; Modified resin and the performance test of matrix material machinery thereof, dielectric properties test, the test of the saturating ripple rate of goods etc.
Result and discussion
1. liquid resin performance characterization
Modified cyanic acid ester resin normal temperature is brown liquid down, and ratio of viscosities is bigger, is about 6.94Pa.s, but reduces rapidly with the rising viscosity of temperature, is that 0.46Pa.s, 60 ℃ of viscositys are 0.21Pa.s as 50 ℃ of viscositys.Modified cyanic acid ester resin 60 ℃ to 160 ℃ very on a large scale in viscosity change smallerly, viscosity is about 0.14Pa.s during as 160 ℃, as shown in figure 11, illustrates that the temperature range that is used in technological operation is bigger.
Figure 12 has provided under the differing temps, and the modified cyanic acid ester resin viscosity is situation over time.As can be seen from the figure below 80 ℃, the viscosity of resin does not change in time.Under 100 ℃, the basic no change of viscosity in the 130min, from 130min to 300min, resin viscosity slowly is increased to 0.4Pa.s from 0.05Pa.s, and viscosity increases sharply afterwards.Under 120 ℃, the basic no change of resin viscosity in the 90min, it is 167min that viscosity is increased to the needed time of 0.4Pa.s, viscosity changes more violent after the 167min.Under 150 ℃, viscosity not region of variation has only about 30min, and viscosity increases sharply afterwards.More than analyze explanation modified resin under the technological operation temperature,, very long time limit of service is arranged,, be very suitable for the enforcement of RTM or winding process easily in process implementing as 80 ℃.Figure 13 shows ripple mast tube figure and adopts silica fiber enhancing modified cyanate ester resin composite material, and the photo after its wound and solidified moulding as shown in figure 13.
Use proof through practice, can reach more than half a year the storage period under the modified cyanic acid ester resin normal temperature.
2. modified cyanic acid ester resin solidifies
The application adopts cyanate ester resin heat polymerization cured resin, according to the curing system that the DSC tracing analysis is determined, adopts infrared spectra respectively modified cyanic acid ester resin to be carried out analyzing relatively through the state of cure of 250 ℃/3h and 280 ℃/3h after fixing.Be respectively the infrared absorption spectra of 250 ℃/3h and 280 ℃/3h after fixing as Figure 14, Figure 15.
Relatively the test result of infrared spectra as can be seen, after 250 ℃/3h and 280 ℃/3h post curing treatment, cyano group 2241cm
-1And 2277cm
-1The charateristic avsorption band at place all disappears, forms the triazine ring absorption peak at 1553cm and solidify the back
-1, 1354cm
-1The place clearly.But through infrared spectrum behind the 280 ℃/3h post curing treatment at 3347cm
-1Near projection has appearred, be the absorption peak of hydroxyl herein, illustrate that post-processing temperature is too high to have caused negative impact.
Carry out soluble part of content measuring of resin to solidifying back resin sample, the result is 97.9%, illustrate that resin adopts 250 ℃/3h curing after, the state of cure of resin is more complete.
3. modified cyanic acid ester performance
3.1 the mechanical property of casting resin
Casting resin preparation: take by weighing quantitative modified cyanic acid ester resin,,, avoid having bubble in the system and the performance that influences casting matrix to eliminate the bubble in the system in 100 ℃ of insulation 1h final vacuums row bubbles 30 minutes (vacuum tightness-more than the 0.09MPa).Then modified cyanic acid ester resin slowly is poured into preheating and scribbles in the stainless steel mould of releasing agent, be cured and cool to the furnace room temperature, preparation casting matrix sample according to the condition of cure of 170 ℃/3h+190 ℃/2h+210 ℃/2h+250 ℃/2h.The Mechanics Performance Testing of casting resin the results are shown in Table 7.
Table 7 modified cyanic acid ester resin casting matrix performance
Tensile strength tensile modulus flexural strength modulus in flexure compressive strength
Test event
(MPa) (GPa) (MPa) (GPa) (MPa)
As a result 37.4 2.74 69 2.82 140
3.2 the dielectric properties of casting resin
The dielectric properties test result of modified resin such as Figure 16 and shown in Figure 17, wherein, Figure 16 shows modified cyanic acid ester resin specific inductivity and frequency relation; Figure 17 shows modified cyanic acid ester resin dielectric loss and frequency relation.As seen from the figure, specific inductivity is between 2.91～2.97, and dielectric loss is applicable to the material of making the saturating ripple of broadband between 0.0001～0.0009.
Claims (10)
1. cyanate resin composition comprises properties-correcting agent and with auto-polymerization mode polymeric tetramethyl-Bisphenol F type cyanate performed polymer, wherein, described properties-correcting agent comprises bisphenol E-type cyanate; The refractive index of described tetramethyl-Bisphenol F type cyanate performed polymer is 1.576～1.582.
2. cyanate resin composition according to claim 1, wherein, the transformation efficiency of cyano group is 32～38% in the described tetramethyl-Bisphenol F type cyanate performed polymer.
3. cyanate resin composition according to claim 1, wherein, the weight ratio of described properties-correcting agent and described tetramethyl-Bisphenol F type cyanate performed polymer is 1: 2～1: 1.
4. cyanate resin composition according to claim 1, wherein, described properties-correcting agent is 30～50 weight % of described composition.
5. method for preparing cyanate resin composition comprises:
A) provide tetramethyl-Bisphenol F type cyanate performed polymer;
B) with properties-correcting agent and the combination of described tetramethyl-Bisphenol F type cyanate performed polymer;
Wherein, described properties-correcting agent comprises bisphenol E-type cyanate.
6. according to the method for claim 5, wherein, step a) is carried out in following condition: make tetramethyl-Bisphenol F type cyanate carry out polymerization, tetramethyl-Bisphenol F type cyanate performed polymer is provided.
7. according to the method for claim 6, described polymeric temperature is 190～220 ℃.
8. according to the method for claim 7, wherein, the refractive index of described tetramethyl-Bisphenol F type cyanate performed polymer is 1.576～1.582; Perhaps, the transformation efficiency of cyano group is 32～38% in the described tetramethyl-Bisphenol F type cyanate performed polymer.
9. according to the method for claim 6, wherein, the weight ratio of described properties-correcting agent and described tetramethyl-Bisphenol F type cyanate performed polymer is 1: 2～1: 1.
10. the goods that comprise the described cyanate resin composition of claim 1.
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| CN102199289B (en) * | 2011-04-08 | 2013-01-02 | 扬州天启化学股份有限公司 | Method for preparing tetramethyl bisphenol F type cyanate resin prepolymer |
| CN103367902B (en) * | 2012-03-30 | 2017-04-19 | 深圳光启创新技术有限公司 | Beautified antenna housing |
| US9879163B2 (en) | 2014-06-06 | 2018-01-30 | General Electric Company | Composition for bonding windings or core laminates in an electrical machine, and associated method |
| CN106810691B (en) * | 2015-11-30 | 2019-08-09 | 航天特种材料及工艺技术研究所 | A method of control cyanate ester resin system rheological property |
| CN111601462B (en) * | 2020-05-18 | 2021-10-22 | 四川九洲电器集团有限责任公司 | High-temperature-resistant and high-dielectric-property copper-clad plate and preparation method thereof and circuit board |
| CN111732728B (en) * | 2020-06-15 | 2022-12-02 | 威海合纵新材料科技有限公司 | Solvent-free winding cyanate ester resin system and preparation method and application thereof |
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