CN103073889A - Flame retardant thermosetting resin and preparation method thereof - Google Patents
Flame retardant thermosetting resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame retardant thermosetting resin and a preparation method thereof. The method comprises the following steps: dissolving hyperbranched polysiloxane containing amino in acetone under the protection of nitrogen, adding a catalyst, pyridine or triethylamine, to obtain a solution; dissolving dichloropentate in acetonitrile and dropwise adding the mixture in the solution for reaction; then washing and filtering to obtain an intumescent flame retardant; and uniformly mixing molten thermally curable resin and the intumescent flame retardant and curing to obtain the flame retardant thermosetting resin. The intumescent flame retardant provided by the invention is of a three-dimensional structure, comprises a lot of active groups and realizes the coexistence of phosphorus, nitrogen and silicon; and the flame retardant thermosetting resin prepared has high thermal stability as well as high char forming characteristic and flame retardancy. The operation process is simple, and the preparation method is wide in applicability, so that the flame retardant thermosetting resin can be applied to mass production.
Description
Technical field
The present invention relates to a kind of thermosetting resin and preparation method thereof, particularly a kind of flame retardant thermoset resins and preparation method thereof.
Background technology
The high-performance thermosetting resin be a class crosslinked have a cancellated macromolecular material, the moulded manufacturability that it is good and physical and mechanical properties (outstanding thermotolerance, mechanical property, erosion resistance etc.) make it occupy indispensable critical role in numerous leading-edge fields such as aerospace, electronic information, electric insulations.Yet, with respect to inorganic materials and metallic substance, the macromolecular material easy firing, inflammableness has become " bottleneck " that restriction high-performance thermosetting resin is used.Therefore, the fire-retardant research of carrying out the high-performance thermosetting resin has important scientific meaning and using value.
Adding fire retardant is the common technology that improves the polymer materials flame retardant resistance.In recent years, expanding fire retardant is widely used in the research and development of flame retarded polymeric material with the outstanding advantage such as its higher flame retarding efficiency, Halogen, few cigarette and environmental friendliness.Expanding fire retardant contains acid source, carbon source, three parts of source of the gas usually.When being heated, carbon source is dewatered under the katalysis of acid source, forms the stable carbon-coating of isolation; The non-combustible gas foaming that source of the gas decompose to produce, thus play fire-retardant effect at burning things which may cause a fire disaster and the cellular expansion carbon-coating of polymkeric substance intermediate formation.
Existing expanding fire retardant mainly contains two large classes, one class is traditional mixed type expanding fire retardant, be acid source such as ammonium polyphosphate, tetramethylolmethane is carbon source, trimeric cyanamide is the Intumescent Retardant System that source of the gas forms, and can be effectively applied to the flame-retardant modified of the thermoplastic polymers such as polypropylene (PP), Low Density Polyethylene (LDPE).This based flame retardant not only addition is larger, and thermostability is lower, usually when being lower than 280 ℃, has just begun to send out the Formed reaction.Another kind of is " trinity " single-component expanding fire retardant, three sources form a molecule by Chemical bond, this type of expanding fire retardant thermostability improves than the mixed type expanding fire retardant, temperature of initial decomposition is at 230 ℃, discharge the temperature of acid source at 290 ℃, can be applied to the flame-retardant modified of engineering plastics such as ABS, PET that processing temperature is higher than 200 ℃.And we know, as bimaleimide resin, the contour performance thermosetting resin of cyanate ester resin, the temperature of aftertreatment is usually greater than 220 ℃ in the solidification process, and the initial heat decomposition temperature of these cured articles itself just is higher than 400 ℃.Obviously, existing expansion type flame retardant is because low thermostability, and is not suitable for being applied to the flame-retardant modified of high-performance thermosetting resin.
Therefore, high-performance thermosetting resin flame-retardant modified had important scientific meaning and using value.
Summary of the invention
The deficiency that exists in order to overcome prior art, the invention reside in provides a kind of Heat stability is good, and has thermosetting resin of high one-tenth carbon and highly effective flame-retardant and preparation method thereof concurrently.
The technical scheme that realization the object of the invention adopts provides a kind of preparation method of flame retardant thermoset resins, may further comprise the steps:
1, under nitrogen protection, by mol, 10 parts of tetramethylolmethanes are joined in 30～100 parts of phosphorus oxychloride, heat by the heating step of 50 ℃/3h+70 ℃/2h+80 ℃/3h, after reaction finishes, through washing, suction filtration, drying obtains dichloropentate;
2, under nitrogen protection, by mol, 10 parts of distilled water and 0.002～0.004 part of catalyst mix are joined in 30～60 parts of alcoholic solvents after evenly, obtain solution A; Under agitation condition, the trialkoxy silane of 2 parts of amido-containing groups slowly is added dropwise in the solution A, be warming up to 50～60 ℃ of reactions 10～12 hours, obtain solution B; Add end-capping reagent in solution B, react after 3～6 hours, through washing, drying, obtaining the degree of branching is 0.83～0.95, and weight-average molecular weight is 8000～11000 the amino hyperbranched polyorganosiloxane that contains; Described catalyzer is hydrochloric acid, sulfuric acid, tosic acid, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, sodium hydroxide or potassium hydroxide;
3, under nitrogen protection, by mol, contain amino hyperbranched polyorganosiloxane with 24～30 parts and be dissolved in 50～100 parts of acetone, add 0.01～0.02 part of catalyzer pyridine or triethylamine, obtain solution C; 10 parts of dichloropentates are dissolved in 50～100 parts of acetonitriles, obtain solution D; Solution D is dropwise joined in the solution C, 50～60 ℃ of lower reactions 6～12 hours, after washing, suction filtration are processed, obtain expanding fire retardant;
4, by mass, thermal curable resin and 5.3～42.9 parts of expanding fire retardants of 100 parts of molten states are mixed, through solidifying, namely obtain a kind of flame retardant thermoset resins.
Described alcoholic solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, the propyl carbinol, or their arbitrary combination.
Described to contain amino trialkoxy silane be a kind of in γ-aminopropyl triethoxysilane, the γ-aminopropyltrimethoxysilane, or their arbitrary combination.
Described thermal curable resin comprises a kind of in self heat-setting resin, resin that self can not thermofixation and the resin system that solidifying agent forms.Self heat-setting resin comprises a kind of in bimaleimide resin and modified resin, cyanate ester resin and the modified resin thereof or their arbitrary combination; The resin system that resin that self can not thermofixation and solidifying agent form comprises Resins, epoxy.
Technical solution of the present invention also comprises a kind of flame retardant thermoset resins that obtains by above-mentioned preparation method.
Compared with prior art, the obtained beneficial effect of the present invention is:
1, expanding fire retardant of the present invention is take the polysiloxane of the high degree of branching that contains a large amount of nitrogen elements as source of the gas, the end group of the hyperbranched polyorganosiloxane by globosity and the dichloropentate of bifunctional head and the tail are in conjunction with forming macromole build (netted) structure, be conducive to strengthen the heat-resisting oxidative stability of each chemical bond in the flame retardant molecule, reach the purpose that improves expanding fire retardant molecular heat stability.
2, flame retardant molecule has a large amount of active groups, has guaranteed to have good reactivity and dispersed with thermosetting resin, can obtain good flame retardant effect under lower aq, reaches the purpose that reduces addition.
3, expanding fire retardant contains a large amount of phosphoric, nitrogen element and element silicon, the effect of performance cooperative flame retardant.
4, starting material of the present invention source is abundant, inexpensive, and preparation technology's suitability is wide, simple to operate.The thermosetting resin of preparation has high one-tenth carbon and highly effective flame-retardant concurrently.
Description of drawings
Fig. 1 is the hyperbranched polyorganosiloxane that the embodiment of the invention 1 provides
29The Si-NMR spectrogram;
Fig. 2 is the infrared spectrum of dichloropentate, hyperbranched polyorganosiloxane, expanding fire retardant in the embodiment of the invention 1;
Fig. 3 is that the expanding fire retardant that the embodiment of the invention 1 provides is made the digital photograph that triketohydrindene hydrate is tested;
Fig. 4 is the structural representation of the expanding fire retardant that provides of the embodiment of the invention 1;
Fig. 5 is the expanding fire retardant that the embodiment of the invention 1 provides
1The H-NMR spectrogram;
Fig. 6 is the expanding fire retardant that the embodiment of the invention 1 provides
31The P-NMR spectrogram;
Fig. 7 is the scanning electron microscope diagram of the expanding fire retardant that provides of the embodiment of the invention 1;
Fig. 8 is respectively thermogravimetric curve figure under air and nitrogen atmosphere of the expanding fire retardant that provides of the embodiment of the invention 1;
Fig. 9 is the digital photograph of expanding fire retardant before and after combustion synthesis in air that the embodiment of the invention 1 provides;
Figure 10 is the limiting oxygen index(LOI) column comparison diagram of the flame-retardant bismaleimide resin of preparation among the bimaleimide resin for preparing in the comparative example of the present invention and the embodiment 1 ~ 4;
Figure 11 is flame-retardant bismaleimide resin thermogravimetric curve figure under air atmosphere of preparation among the bimaleimide resin for preparing in the comparative example of the present invention and the embodiment 1 ~ 4;
Figure 12 is be heated under the differing temps digital photograph of carbon residue behind the 15min of the flame-retardant bismaleimide resin of preparation among the bimaleimide resin for preparing in the comparative example of the present invention and the embodiment 2.
Embodiment
Below in conjunction with accompanying drawing, embodiment and comparative example, technical solution of the present invention will be further described.
1, the preparation of expanding fire retardant
(1) under nitrogen protection, the 13.6g tetramethylolmethane joins in the 90mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 81.5%.
(2) under nitrogen protection and normal temperature, add 9g deionized water, 50mL ethanol and 0.5mL tetraethyl ammonium hydroxide (20% the aqueous solution) in the 250mL reactor, stir, obtain uniform mixed solution.Adopt constant pressure funnel in reactor, to drip the 22.1g γ-aminopropyl triethoxysilane, dropwise in the 10min.After being warming up to 50 ℃ of reaction 10h, in reactor, add again hexamethyldisilane, continue reaction 6 hours, obtain the solution of clear.Through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching is 0.85, and molecular weight is 9000, and amino content is 0.1mol.Its
29Si-NMR spectrogram and infrared spectrum are seen respectively Fig. 1 and 2.
(3) in the 250mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.024mol is dissolved in the 50mL acetone with above-mentioned amino content.The dichloropentate of 0.01mol present embodiment preparation is dissolved in the 50mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 0.1mL pyridine, progressively heat up, make flask internal reaction thing at 50 ℃ of lower reaction 8h.Reaction is used N after finishing, and N-METHYLFORMAMIDE washing 3 times is used washing with acetone 3 times again, and suction filtration is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 79.3%.Its infrared spectrum, drip digital photograph behind the triketohydrindene hydrate, structural representation,
1The H-NMR spectrogram,
31P-NMR spectrogram, scanning electron microscope diagram, the thermogravimetric curve under air and nitrogen atmosphere are seen respectively accompanying drawing 2,3,4,5,6,7 and 8.
Referring to accompanying drawing 1, it is the hyperbranched polyorganosiloxane that contains amino that present embodiment provides
29The Si-NMR spectrogram.Existence at the strong absorption peak at-68.8ppm place shows that siloxanes has formed a large amount of branching links, the degree of branching 0.85 of synthesis of super branched polysiloxane by can be calculated by hydrolytic condensation.The degree of branching of superelevation provides structural framing for the expanding fire retardant that forms the three-dimensional bodily form (netted) structure.Its weight-average molecular weight is 9000.
Referring to accompanying drawing 2, it is dichloropentate, the hyperbranched polyorganosiloxane that contains amino and the infrared spectrum of expanding fire retardant that present embodiment provides.Can find out that the infrared spectrum of expanding fire retardant is at 1085cm
-1There is the characteristic absorbance peak-to-peak of strong P-N key at the place, shows that chemical reaction has occured for dichloropentate and the hyperbranched polyorganosiloxane that contains amino.In addition, also there are 3400 cm in spectrogram
-1With 1600 cm
-1Absorption peak, show and still contain the amino group that has neither part nor lot in reaction in the fire retardant that is synthesized.This can also be confirmed by the colourless mauve digital photograph (referring to accompanying drawing 3) that becomes after expanding fire retardant drips triketohydrindene hydrate.This provides guarantee for the expanding fire retardant modified heat convertible resin.
Referring to accompanying drawing 4, it is the structural representation of fire retardant provided by the invention.The hyperbranched polyorganosiloxane head and the tail that contain a large amount of end groups that being configured as of expanding fire retardant contained the dichloropentate molecule of bifunctional and globosity in conjunction with and a kind of tridimensional network of forming.Compare the expanding fire retardant of existing single linear structure, each chemical bond in the designed synthetic flame retardant molecule since the netted heat-resisting oxidative stability that links to each other strengthen, thereby improved expandable flame retardant agent molecule heat-resistant stability.A large amount of active groups of build molecular end are conducive to improve the consistency of flame retardant molecule and polymeric matrix simultaneously.
Referring to accompanying drawing 5, it is the expanding fire retardant that present embodiment provides
1The H-NMR spectrogram.In the spectrogram, fignal center at chemical shift 1.3ppm, 1.6ppm, 2.4ppm, 3.8ppm place has shown the existence of aminopropyl active function groups in the expanding fire retardant, chemical shift 6.5ppm place fignal center is the absorption peak of H on the phosphamide key, has shown the generation of P-N key.
Referring to accompanying drawing 6, it is the solid of the expanding fire retardant that provides of present embodiment
31The P-NMR spectrogram.In the spectrogram, the chemical shift of P appears at the 7.24ppm place, shows that P-Cl and amino reaction generate the P-N key; And the ability of N atom feedback electronics is lower, so that the chemical shift of P is mobile to low.
Referring to accompanying drawing 7, it is the scanning electron microscope diagram of the expanding fire retardant that provides of present embodiment.Can find out that the configuration of this fire retardant is that the dichloropentate molecule is that bridge links formation three dimensional structure (reticulated structure) with the microspheroidal hyperbranched polyorganosiloxane.
Referring to table 1, it is the ultimate analysis EDS table of the expanding fire retardant that provides of present embodiment.Therefrom the atomicity ratio of P and N is about 1:1 as can be known, shows P-Cl and contains amino hyperbranched polyorganosiloxane most of NH at end
2-reacting, remainder amino has neither part nor lot in reaction.
Table 1: the EDS data of expanding fire retardant
Referring to accompanying drawing 8 and table 2, it is the respectively thermogravimetric curve under air and nitrogen atmosphere and the corresponding data list of expanding fire retardant that present embodiment provides.At N
2Temperature of initial decomposition (T with expanding fire retardant under the air atmosphere
Di, the temperature of weightless 5wt%) and be respectively 297.5 ℃ and 298.1 ℃, the first decomposition mechanism peak temperature (T
Max1) be respectively 325.2 ℃ and 320.1 ℃, illustrate that expanding fire retardant shows similar thermal decomposition behavior in two kinds of atmosphere.Be worth pointing out that expanding fire retardant begins to decompose usually about 230 ℃ in the prior art, therefore, the expanding fire retardant of the present invention's preparation has overcome the low deficiency of thermostability that prior art exists.On the other hand, generally, because the effect of oxygen in the air, high molecular thermo-oxidative stability will be lower than it at N
2Thermostability.Intermolecular chemical bond when being heated is because oxygenizement easy fracture more, so decomposition temperature can compare N usually
2Low in the atmosphere.The expanding fire retardant that embodiment 1 provides is then similar at the lower thermal decomposition characteristic of two kinds of atmosphere, and this characteristic is very favourable to using.The reason that this phenomenon occurs is that the molecular linkage of expanding fire retardant of the present invention links to each other with web form, makes it have the resistance of oxidation that is better than the conventional linear molecule in thermal process.Merit attention, at air and N
2Expanding fire retardant is 800 under the atmosphere
oThe carbon residue weight of C is respectively 62.4% and 53.5%, illustrates that oxygen has participated in the formation of expansion carbon-coating, and this is very favourable for the flame retardant resistance that improves material.In addition, 62.4% high carbon residue scale understands the good one-tenth carbon of expanding fire retardant, for the development of flame retardant thermoset resins provides and can reliably guarantee.
Table 2: the heat analysis data of expanding fire retardant
Referring to accompanying drawing 9, it is the digital photograph of expanding fire retardant before and after combustion synthesis in air that present embodiment provides.Can find out that this expanding fire retardant has good swelling property and becomes carbon, when being expected at burning, it will form barrier layer protection resin matrix at polymer surfaces, play fire-retardant effect.
Above performance data shows that the expanding fire retardant that present embodiment provides has high thermostability, swelling property and becomes carbon, contains simultaneously a large amount of active groups, for the preparation of flame retardant thermoset resins provides assurance.
2, the preparation of flame-retardant bismaleimide resin
Take by weighing 45.7g N, N '-4,4 '-diphenyl methane dimaleimide and 34.3g O, O '-diallyl bisphenol at 135 ℃ of lower mechanical stirring pre-polymerization 15min, obtain the transparent clarified liq of brown color in beaker.Add the expanding fire retardant (accounting for the 5wt% of resin system total mass) of 4.21g embodiment 1 preparation in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get a kind of flame-retardant bismaleimide resin.Its limiting oxygen index(LOI), thermogravimetric curve and heat analysis data are seen respectively ginseng Figure 10,11 and table 3.
Take by weighing 45.7g N, N '-4,4 '-diphenyl methane dimaleimide and 34.3g O, O '-diallyl bisphenol at 135 ℃ of lower mechanical stirring pre-polymerization 15min, obtain the transparent clarified liq of brown color in beaker; Add the expanding fire retardant (accounting for the 10wt% of resin system total mass) of 8.89g embodiment 1 preparation in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get a kind of flame-retardant bismaleimide resin.Its limiting oxygen index(LOI), thermogravimetric curve and heat analysis data are respectively referring to accompanying drawing 10,11 and table 3.
Take by weighing 45.7g N, N '-4,4 '-diphenyl methane dimaleimide and 34.3g O, O '-diallyl bisphenol at 135 ℃ of lower mechanical stirring pre-polymerization 15min, obtain the transparent clarified liq of brown color in beaker; Add the expanding fire retardant (accounting for the 15wt% of resin system total mass) of 14.1g embodiment 1 preparation in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get a kind of flame-retardant bismaleimide resin.Its limiting oxygen index(LOI), thermogravimetric curve and heat analysis data are respectively referring to accompanying drawing 10,11 and table 3.
Embodiment 4
Take by weighing 45.7g N, N '-4,4 '-diphenyl methane dimaleimide and 34.3g O, O '-diallyl bisphenol at 135 ℃ of lower mechanical stirring pre-polymerization 15min, obtain the transparent clarified liq of brown color in beaker; Add the expanding fire retardant (accounting for the 20wt% of resin system total mass) of 20g embodiment 1 preparation in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get a kind of flame-retardant bismaleimide resin.Its limiting oxygen index(LOI), thermogravimetric curve and heat analysis data are respectively referring to accompanying drawing 10,11 and table 3.
Comparative example, the preparation of bimaleimide resin: take by weighing 40g N, N '-4,4 '-diphenyl methane dimaleimide and 30g O, O '-diallyl bisphenol at 135 ℃ of lower pre-polymerization 30min that stir, obtains the transparent clarified liq of brown color (prepolymer) in beaker.This prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get the bismaleimides cured resin.Its limiting oxygen index(LOI), thermogravimetric curve and heat analysis data are respectively referring to accompanying drawing 10,11 and table 3.
Referring to accompanying drawing 10, it is the limiting oxygen index(LOI) column comparison diagram of flame-retardant bismaleimide resin of bimaleimide resin, embodiment 1～4 preparation of comparative example preparation, the adding of expanding fire retardant makes the limiting oxygen index(LOI) value of bimaleimide resin that raising in various degree arranged, and along with the expanding fire retardant addition increases, limiting oxygen index(LOI) improves degree and increases gradually.When the addition of expanding fire retardant is 20 wt%, the limiting oxygen index(LOI) of flame-retardant bismaleimide resin is 33.8, be higher than the analog value of the bimaleimide resin of comparative example preparation, show that expanding fire retardant demonstrates good flame retardant properties to bimaleimide resin.
Referring to accompanying drawing 11, it is the bimaleimide resin of comparative example preparation, the thermogravimetric curve of flame-retardant bismaleimide resin under air atmosphere of embodiment 1～4 preparation, and table 3 is the bimaleimide resin of comparative example preparation and the heat analysis data of the flame-retarded resin that embodiment 1～4 prepares.
Table 3: heat analysis data
By reference to the accompanying drawings 10,11 and table 3 can see, bimaleimide resin and flame-retardant bismaleimide resin all have two main catabolic phases, and near 425 ℃ that first catabolic phase all occurs, and the flame-retardant bismaleimide resin of second catabolic phase embodiment preparation exceeds 50 ℃ than the value of the bimaleimide resin of comparative example preparation, can infer thus, at the initial catabolic phase of flame-retarded resin, expanding fire retardant divides three sources of explanation, thereby between resin matrix and burning things which may cause a fire disaster, formed stable barrier layer, strengthened the thermostability of modified resin at hot stage.The carbon residue weight of testing simultaneously gained all will exceed theoretical carbon residue and show; exist mutually collaborative effect between expanding fire retardant and the bimaleimide resin; high carbon residue scale understands that bimaleimide resin can be difficult to further burning under the protection of stablizing carbon-coating, is the notable feature that flame retardant properties improves.
Referring to accompanying drawing 12, it is be heated under the differing temps digital photograph of corresponding resin behind the 15min of the flame-retardant bismaleimide resin of the bimaleimide resin of comparative example preparation and embodiment 2 preparations, can be clear that, the bimaleimide resin of comparative example preparation is when being heated, resin mass constantly swells, so that resin surface is exposed on the burning things which may cause a fire disaster more, accelerated the burning of resin.Behind the 15min that is heated under 650 ℃, resin almost burns totally.Corresponding with it, the flame-retardant bismaleimide resin of embodiment 2 preparations is in being subjected to thermal process, and the surface forms the graphite carbon-coating of stable fragrant condensed ring, has greatly increased the thermostability of modified resin.Modified resin is behind the 15min that is heated under 650 ℃; except volumetric expansion is original 3 times; can also keep complete block complexion; the carbon residue amount is especially up to 40.12%; show thus in combustion processes; expanding fire retardant can form stable barrier layer protection resin matrix at resin surface really, thereby significantly plays fire-retardant effect.
Above-mentioned data show that bimaleimide resin disclosed by the invention is a kind of flame retardant thermoset resins.
1, the preparation of expanding fire retardant
(1) under nitrogen protection, the 6.8g tetramethylolmethane joins in the 45mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 79.5%.
(2) nitrogen protection under the normal temperature, adds 18g deionized water, 50mL methyl alcohol and 1mL tetraethyl ammonium hydroxide (20% the aqueous solution) in the 250mL reactor, stir, and obtains uniform mixed solution.Adopt constant pressure funnel in reactor, to drip the 44.2g γ-aminopropyl triethoxysilane, dropwise in the 10min.Behind 50 ℃ of reaction 12h, add the end-capping reagent hexamethyldisilane in reactor again, continue reaction 6 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching: 0.95, weight-average molecular weight: 11000, amino content is 0.2mol.
(3) in the 250mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.05mol is dissolved in the 50mL acetone with above-mentioned amino content.0.02mol the dichloropentate of present embodiment preparation is dissolved in the 50mL acetonitrile, forms acetonitrile solution, by constant pressure funnel, drips acetonitrile solution in flask, is added dropwise to complete in half an hour.Then, drip the 0.25mL pyridine in flask, progressively heating up makes the interior temperature of flask reach 50 ℃, reaction 6h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 70.3%.
2, the preparation of flame-retardant bismaleimide resin
Take by weighing 45.7g N, in beaker, mechanical stirring pre-polymerization 15min obtains the transparent clarified liq of brown color under 135 ℃ for N '-4,4 '-diphenyl methane dimaleimide and 34.3g O, O '-diallyl bisphenol; Add the expanding fire retardant of 10g embodiment 5 preparations in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get a kind of flame-retardant bismaleimide resin.
1, expanding fire retardant is synthetic
(1) under nitrogen protection, the 13.6g tetramethylolmethane joins in the 45mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 69.7%.
(2) under nitrogen protection, add 4.5g deionized water, 50mL ethanol and 0.5mL Tetramethylammonium hydroxide (20% the aqueous solution) in the 250mL reactor, stir, obtain uniform mixed solution.Adopt constant pressure funnel in there-necked flask, to drip the 11g γ-aminopropyl triethoxysilane, dropwise in the 10min.Behind 50 ℃ of reaction 10h, add the end-capping reagent hexamethyldisilane in reactor again, continue reaction 5 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching: 0.83, weight-average molecular weight: 8000, amino content is 0.05mol.
(3) in the 250mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.03mol is dissolved in the 50mL acetone with above-mentioned amino content.0.01mol the dichloropentate of present embodiment preparation is dissolved in the 50mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 0.1mL pyridine, progressively heat up, make flask internal reaction thing at 50 ℃ of lower reaction 8h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 75.6%.
2, the preparation of fire-retardant cyanate ester resin
Take by weighing the 30g bisphenol A cyanate ester in beaker, 150 ℃ of lower mechanical stirring, treat that cyanate dissolves fully, obtains clarified liq; Add the expanding fire retardant of 3.50g embodiment 6 preparations in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 150 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h technique respectively again, namely get fire-retardant cyanate ester resin.
1, expanding fire retardant is synthetic
(1) under nitrogen protection, the 27.2g tetramethylolmethane joins in the 180mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 78.5%.
(2) nitrogen protection under the normal temperature, adds 27g deionized water, 50mL propyl alcohol and 2mL tetraethyl ammonium hydroxide (20% the aqueous solution) in the 250mL reactor, stir, and obtains uniform mixed solution.Adopt constant pressure funnel in reactor, to drip the 66.3g γ-aminopropyl triethoxysilane, dropwise in the 10min.After being warming up to 55 ℃ of reaction 10h, add the end-capping reagent hexamethyldisilane in reactor again, continue reaction 6 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching: 0.84, weight-average molecular weight: 9000, amino content is 0.3mol.
(3) in the 250mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.075mol is dissolved in the 60mL acetone with above-mentioned amino content.0.03mol the dichloropentate of present embodiment preparation is dissolved in the 50mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 0.5mL pyridine, progressively heat up, make flask internal reaction thing at 56 ℃ of lower reaction 8h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 74.3%.
2, the preparation of fire-retardant cyanate/bimaleimide resin
Take by weighing 40g N, N '-4,4 '-diphenyl methane dimaleimide and 40g dicyclopentadiene type ethylene rhodanate are in beaker, 150 ℃ of lower mechanical stirring; After resin dissolves fully, obtain clarified liq; Add the expanding fire retardant of 18.6g embodiment 7 preparations in liquid, mechanical stirring 30min obtains prepolymer.Prepolymer is poured in the preheated mould, under 150 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h technique respectively again, namely get fire-retardant cyanate/bimaleimide resin.
1, expanding fire retardant is synthetic
(1) under nitrogen protection, the 20.4g tetramethylolmethane joins in the 150mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 77.3%.
(2) nitrogen protection, under the normal temperature, adding 36g deionized water, 100mL propyl carbinol and 4.5g pH are 10 NaOH solution in the 500mL reactor, stir, and obtain uniform mixed solution.Adopt constant pressure funnel in reactor, to drip the 88.4g γ-aminopropyl triethoxysilane, dropwise in the 10min.After being warming up to 50 ℃ of reaction 12h, add the end-capping reagent hexamethyldisilane in reactor again, continue reaction 5 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching: 0.9, weight-average molecular weight: 9500, amino content is 0.4mol.
(3) in the 500mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.25mol is dissolved in the 100mL acetone with above-mentioned amino content.0.1mol the dichloropentate of present embodiment preparation is dissolved in the 100mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 1.5mL triethylamine, progressively heat up, make flask internal reaction thing at 60 ℃ of lower reaction 8h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 69.5%.
2, the preparation of fire retarding epoxide resin
Take by weighing 75g bisphenol A type epoxy resin (trade mark E-51) in beaker, be heated to 70 ℃ and make it to become low-viscosity (mobile) liquid, add the expanding fire retardant of 20g embodiment 8 preparations, the 3g 2-ethyl-4-methylimidazole, mechanical stirring 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 70 ℃, vacuumized 20min, carry out thermofixation according to 80 ℃/2h+100 ℃/2h+120 ℃/2h and 140 ℃/4h technique, namely get fire retarding epoxide resin.
Embodiment 9
1, expanding fire retardant is synthetic
(1) under nitrogen protection, the 34g tetramethylolmethane joins in the 220mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 77.8%.
(2) nitrogen protection adds 45g deionized water, 150mL n-propyl alcohol and 6g2.2g pH and is 10 KOH solution in the 500mL reactor under the normal temperature, stir, and obtains uniform mixed solution.Adopt constant pressure funnel in reactor, to drip 55g γ-aminopropyl triethoxysilane and 45g γ-aminopropyltrimethoxysilane, dropwise in the 10min.Behind 50 ℃ of reaction 12h, add the end-capping reagent hexamethyldisilane in reactor again, continue reaction 6 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching is 0.92, and weight-average molecular weight is 9500, and amino content is 0.5mol.
(3) in the 500mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.3mol is dissolved in the 150mL acetone with above-mentioned amino content.0.12mol the dichloropentate of present embodiment preparation is dissolved in the 100mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 1.2mL triethylamine, progressively heat up, make flask internal reaction thing at 56 ℃ of lower reaction 8h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 70.2%.
2, the preparation of fire-retardant ethylene rhodanate/epoxide resin
Take by weighing 20g bisphenol A type epoxy resin and 60g bisphenol A cyanate in beaker, 150 ℃ of lower mechanical stirring, treat that resin dissolves fully, obtains clarified liq; Add the expanding fire retardant of 18g embodiment 9 preparations in liquid, mechanical stirring pre-polymerization 25min obtains prepolymer.Prepolymer is poured in the preheated mould, under 150 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h technique respectively again, namely get fire-retardant ethylene rhodanate/epoxide resin.
1, expanding fire retardant is synthetic
(1) under nitrogen protection, the 6.8g tetramethylolmethane joins in the 90mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 82.7%.
(2) nitrogen protection under the normal temperature, adds 9g deionized water, 50mL ethanol, 50mL methyl alcohol and 0.5mL Tetramethylammonium hydroxide (20% the aqueous solution) in the 250mL reactor, stir, and obtains uniform mixed solution.Adopt constant pressure funnel in reactor, to drip the 17.9g γ-aminopropyltrimethoxysilane, dropwise in the 10min.After being warming up to 55 ℃ of reaction 10h, add the end-capping reagent hexamethyldisilane in reactor again, continue reaction 5 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching is 0.86, and weight-average molecular weight is 8600, and amino content is 0.1mol.
(3) in the 250mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.027mol is dissolved in the 80mL acetone with above-mentioned amino content.0.01mol the dichloropentate of present embodiment preparation is dissolved in the 100mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 0.1mL triethylamine, make flask internal reaction thing at 60 ℃ of lower reaction 8h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 78.6%.
2, the preparation of fire-retardant bismaleimides/bisphenol A cyanate resin
Take by weighing 40gN, N '-4,4 '-diphenyl methane dimaleimide and 7.5g bisphenol A cyanate 135 ℃ of lower mechanical stirring, treat that resin dissolves fully, obtains clarified liq in beaker; Add the expanding fire retardant of 8.50g embodiment 10 preparations in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 30min, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get fire-retardant Bismaleimide-Cyanate Ester Resin resin.
Embodiment 11
1, expanding fire retardant is synthetic
(1) under nitrogen protection, the 13.6g tetramethylolmethane joins in the 150mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 83.6%.
(2) under nitrogen protection, adding 18g deionized water, 30mL methyl alcohol, 50mL propyl alcohol and 4.5g pH are 10 KOH solution in the 250mL there-necked flask, stir, and obtain uniform mixed solution.Adopt constant pressure funnel in interpreter, to drip 17.9g γ-aminopropyltrimethoxysilane and 22.1g γ-aminopropyl triethoxysilane, dropwise in the 10min.Behind 60 ℃ of reaction 10h, add the end-capping reagent hexamethyldisilane in reactor again, continue reaction 6 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching is 0.84, and weight-average molecular weight is 8500, and amino content is 0.2mol.
(3) in the 250mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.03mol is dissolved in the 100mL acetone with above-mentioned amino content.0.012mol the dichloropentate of present embodiment preparation is dissolved in the 50mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 0.1mL pyridine, progressively heat up, make flask internal reaction thing at 60 ℃ of lower reaction 6h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 70%.
2, the preparation of flame-retardant bismaleimide resin
Take by weighing 45.7g N, in beaker, mechanical stirring pre-polymerization 15min obtains the transparent clarified liq of brown color under 135 ℃ for N '-4,4 '-diphenyl methane dimaleimide and 34.3g O, O '-diallyl bisphenol; Add the expanding fire retardant of 24g embodiment 11 preparations in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get flame-retardant bismaleimide resin.
Embodiment 12
1, expanding fire retardant is synthetic
(1) under nitrogen protection, the 6.8g tetramethylolmethane joins in the 100mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 80.5%.
(2) nitrogen protection, under the normal temperature, adding 27g deionized water, 50mL ethanol, 100mL n-propyl alcohol and 3.6g pH are 2 HCl solution in the 500mL reactor, stir, and obtain uniform mixed solution.Adopt constant pressure funnel in reactor, to drip the 53.7g γ-aminopropyltrimethoxysilane, dropwise in the 10min.After being warming up to 60 ℃ of reaction 10h, add the end-capping reagent hexamethyldisilane in reactor again, continue reaction 3 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching is 0.83, and weight-average molecular weight is 8300, and amino content is 0.3mol.
(3) in the 500mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.1mol is dissolved in the 100mL acetone with above-mentioned amino content.0.04mol the dichloropentate of present embodiment preparation is dissolved in the 150mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 0.5mL triethylamine, progressively heat up, make flask internal reaction thing at 60 ℃ of lower reaction 8h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 74.3%.
2, the preparation of flame-retardant bismaleimide resin
Take by weighing 45.7g N, in beaker, mechanical stirring pre-polymerization 15min obtains the transparent clarified liq of brown color under 135 ℃ for N '-4,4 '-diphenyl methane dimaleimide and 34.3g O, O '-diallyl bisphenol; Add the expanding fire retardant of 27 embodiment, 12 preparations in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get flame-retardant bismaleimide resin.
Embodiment 13
1, expanding fire retardant is synthetic
(1) under nitrogen protection, the 20.4g tetramethylolmethane joins in the 200mL phosphorus oxychloride, then progressively is warming up to 80 ℃ of reaction 8h.Reaction is washed three times successively with tetracol phenixin and ethanol after finishing, suction filtration, and vacuum-drying gets the white powder product, and productive rate is 84.3%.
(2) nitrogen protection, under the normal temperature, adding 36g deionized water, 50mL propyl alcohol, 100mL propyl carbinol and 5g pH are 2 HCl solution in the 500mL reactor, stir, and obtain uniform mixed solution.Adopt constant pressure funnel in reactor, to drip the 88.4g γ-aminopropyltrimethoxysilane, dropwise in the 10min.Behind 50 ℃ of reaction 12h, add the end-capping reagent hexamethyldisilane again, continue reaction 6 hours, obtain the solution of clear, through the Rotary Evaporators underpressure distillation, obtain light yellow thick liquid, it is to contain amino hyperbranched polyorganosiloxane.The degree of branching is 0.87, and weight-average molecular weight is 9600, and amino content is 0.4mol.
(3) in the 250mL four-hole boiling flask, be that the hyperbranched polyorganosiloxane of 0.13mol is dissolved in the 100mL acetone with above-mentioned amino content.0.05mol the dichloropentate of present embodiment preparation is dissolved in the 50mL acetonitrile, forms acetonitrile solution.By constant pressure funnel, in flask, drip acetonitrile solution, within half an hour, be added dropwise to complete.Then, in flask, drip the 0.1mL pyridine, progressively heat up, make flask internal reaction thing at 60 ℃ of lower reaction 10h.Reaction is used N after finishing, and N-2 methylformamide washing 3 times is used washing with acetone 3 times again, behind the suction filtration, is dried to constant weight in 80 ℃.Product is buff powder, and productive rate is 78.3%.
2, the preparation of flame-retardant bismaleimide resin
Take by weighing 45.7g N, in beaker, mechanical stirring pre-polymerization 15min obtains the transparent clarified liq of brown color under 135 ℃ for N '-4,4 '-diphenyl methane dimaleimide and 34.3g O, O '-diallyl bisphenol; Add the expanding fire retardant of 34.3g embodiment 5 preparations in liquid, mechanical stirring pre-polymerization 15min obtains prepolymer.Prepolymer is poured in the preheated mould, under 135 ℃, vacuumized 1h, be cured and aftertreatment according to 150 ℃/2h+180 ℃/2h+200 ℃/2h+220 ℃/2h and 230 ℃/4h technique respectively again, namely get flame-retardant bismaleimide resin.
Claims (7)
1. the preparation method of a flame retardant thermoset resins is characterized in that may further comprise the steps:
(1) under nitrogen protection, by mol, 10 parts of tetramethylolmethanes are joined in 30～100 parts of phosphorus oxychloride, heat by the heating step of 50 ℃/3h+70 ℃/2h+80 ℃/3h, after reaction finishes, through washing, suction filtration, drying obtains dichloropentate;
(2) under nitrogen protection, by mol, 10 parts of distilled water and 0.002～0.004 part of catalyst mix are joined in 30～60 parts of alcoholic solvents after evenly, obtain solution A; Under agitation condition, the trialkoxy silane of 2 parts of amido-containing groups slowly is added dropwise in the solution A, be warming up to 50～60 ℃ of reactions 10～12 hours, obtain solution B; Add end-capping reagent in solution B, react after 3～6 hours, through washing, drying, obtaining the degree of branching is 0.83～0.95, and weight-average molecular weight is 8000～11000 the amino hyperbranched polyorganosiloxane that contains; Described catalyzer is hydrochloric acid, sulfuric acid, tosic acid, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, sodium hydroxide or potassium hydroxide;
(3) under nitrogen protection, by mol, contain amino hyperbranched polyorganosiloxane with 24～30 parts and be dissolved in 50～100 parts of acetone, add 0.01～0.02 part of catalyzer pyridine or triethylamine, obtain solution C; 10 parts of dichloropentates are dissolved in 50～100 parts of acetonitriles, obtain solution D; Solution D is dropwise joined in the solution C, 50～60 ℃ of lower reactions 6～12 hours, after washing, suction filtration are processed, obtain expanding fire retardant;
(4) by mass, thermal curable resin and 5.3～42.9 parts of expanding fire retardants of 100 parts of molten states are mixed, through solidifying, namely obtain a kind of flame retardant thermoset resins.
2. the preparation method of a kind of flame retardant thermoset resins according to claim 1 is characterized in that: described alcoholic solvent is a kind of in methyl alcohol, ethanol, propyl alcohol, the propyl carbinol, or their arbitrary combination.
3. the preparation method of a kind of flame retardant thermoset resins according to claim 1, it is characterized in that: described to contain amino trialkoxy silane be a kind of in γ-aminopropyl triethoxysilane, the γ-aminopropyltrimethoxysilane, or their arbitrary combination.
4. the preparation method of a kind of flame retardant thermoset resins according to claim 1 is characterized in that: described thermal curable resin comprises a kind of in self heat-setting resin, resin that self can not thermofixation and the resin system that solidifying agent forms.
5. the preparation method of a kind of flame retardant thermoset resins according to claim 4, it is characterized in that: described self heat-setting resin comprises a kind of in bimaleimide resin and modified resin, cyanate ester resin and the modified resin thereof or their arbitrary combination.
6. the preparation method of a kind of flame retardant thermoset resins according to claim 4 is characterized in that: described self can not thermofixation resin and the resin system that solidifying agent forms comprise Resins, epoxy.
7. a kind of flame retardant thermoset resins that obtains by preparation method claimed in claim 1.
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| CN107868254A (en) * | 2017-12-14 | 2018-04-03 | 成都硅宝科技股份有限公司 | A kind of Multifunctional plastic additive and preparation method thereof |
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| CN110628000A (en) * | 2019-09-11 | 2019-12-31 | 西北工业大学 | High-toughness flame-retardant medium-low temperature cured epoxy resin system and preparation method thereof |
| CN111739682A (en) * | 2020-07-31 | 2020-10-02 | 安徽华电线缆股份有限公司 | High-frequency high-anti-interference communication cable based on 5G base station and production method |
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