CN102838779B - Composite expandable flame retardant modified thermosetting resin and preparation method thereof - Google Patents
Composite expandable flame retardant modified thermosetting resin and preparation method thereof Download PDFInfo
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- CN102838779B CN102838779B CN201210346338.3A CN201210346338A CN102838779B CN 102838779 B CN102838779 B CN 102838779B CN 201210346338 A CN201210346338 A CN 201210346338A CN 102838779 B CN102838779 B CN 102838779B
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Abstract
The invention discloses composite expandable flame retardant modified thermosetting resin and a preparation method thereof. The preparation method comprises the following steps of: adding mixed solution of phosphorus oxychloride and dioxane into suspension liquid of expandable graphite and dioxane which are evenly mixed, adding polyol and catalyst, then adding 1, 3, 5-triglycidyl isocyanurate, and after reaction is ended, conducting suction filtration, washing and drying to obtain composite expandable flame retardant which contains phosphorous organic expandable flame retardant which covers the surface of inorganic expandable graphite in a chemical bonding way; and evenly mixing thermosetting resin and the composite expandable flame retardant according to weight ratio of 95:5 to 80:20 at the melting temperature of the resin to obtain the composite expandable flame retardant modified thermosetting resin. On the premise that the modified resin reserves the excellent heat resistance of the thermosetting resin, the modified resin has excellent flame retardant performance. The preparation method provided by the invention has the characteristics of high applicability, simple operation process and high flame retardant performance.
Description
Technical field
The present invention relates to flame retarded polymeric material technical field, be specifically related to a kind of compound expanding fire retardant modified heat convertible resin and preparation method thereof.
Background technology
High-performance thermosetting resin is important foundation material indispensable in modern industry field.But the flame retardant resistance of existing high-performance thermosetting resin still can not meet service requirements.Therefore, how, on the basis of premium properties that keeps existing high-performance thermosetting resin, obtain the focus that outstanding flame retardant resistance becomes current material development field.
The flame retardant resistance that improves polymer materials by adding fire retardant is a very effective approach.Expanding fire retardant (IFR) is a kind of efficient halogen-free flame retardants, has low cigarette, low toxicity, low-corrosiveness and nothing and melt advantages such as dripping drippage in combustion processes, has therefore caused everybody extensive concern.Expansion type flame retardant can be divided into two kinds of chemically expansible fire retardant and physical expansion fire retardants.So far, people have prepared a lot of expanding fire retardant modified heat convertible resins.But, it is found that, there are some bottleneck problems in these systems.First, to with phosphorus, nitrogen, carbon is the chemically expansible fire retardant of main nucleus, although its flame retardant effect is good, but need very high addition, the interpolation of fire retardant simultaneously often causes the decline of the resins such as thermal characteristics and mechanical property, and in the process of using in processing, there is migration or the problem such as separate out (referring to document: Modesti M, Lorenzetti A, Simioni F, Camino G. Expandable graphite as an intumescent flame retardant in polyisocyanurate – polyurethane foams. Polymer Degradation and Stability. 2002, 77:195-202.).Secondly, the most frequently used physical expanding fire retardant is expansible black lead (EG), and its fire retardant mechanism is that the expansion thermal insulation layer that expansion forms by own vol delays or suppresses to burn and degraded.But, between this based flame retardant and polymkeric substance, do not occur or rare chemical action, and the adhesive power between the vermiform charcoal layer forming a little less than, the charcoal layer of formation easily destroys.In addition; due to and resin between bonding force a little less than; not only can cause declining to a great extent of resin matrix mechanical property; but also exist " candle wick " effect (referring to document: Zhu HF; Zhu QL, Li J, Tao K; Xue LX, Yan Q. Synergistic effect between expandable graphite and ammonium polyphosphate on flame retarded polylactide. Polymer Degradation and Stability. 2011; 96:183-9.).Therefore, limited the widespread use of EG.
In order to overcome the problems referred to above, people mix two kinds of expansion type flame retardants composite, utilize both mixture to improve the flame retardant resistance of polymkeric substance.Research work shows; under identical addition, the expandable flame retardant agent composition of two types has more excellent flame retardant resistance (referring to document: Zhu HF than independent chemically expansible fire retardant or physical expansion fire retardant; Zhu QL; Li J; Tao K; Xue LX, Yan Q. Synergistic effect between expandable graphite and ammonium polyphosphate on flame retarded polylactide. Polymer Degradation and Stability. 2011; 96:183-9.).But, two kinds of expanding fire retardants are mixed and still have many problems.First, physical mixed, makes more difficult good dispersiveness and the interface interaction power of obtaining in organic matrix of physical fire retardant, affects the performance of flame retardant properties.Secondly, in order to obtain good flame retardant effect, chemically expansible fire retardant needs higher addition conventionally, and the thermotolerance of material is reduced.(referring to document: Gao F; Tong LF, Fang ZP. Effect of a novel phosphorous – nitrogen containing intumescent flame retardant on the fire retardancy and the thermal behaviour of poly (butylene terephthalate). Polymer Degradation and Stability. 2006; 91:1295-9.)
Summary of the invention
The deficiency existing in order to overcome prior art, the object of this invention is to provide and a kind ofly keeping, on the stable on heating basis of thermosetting resin, having performance resins of good flame retardant properties and preparation method thereof simultaneously.
In order to reach foregoing invention object, the technical solution used in the present invention is to provide a kind of preparation method of compound expanding fire retardant modified heat convertible resin, comprises the steps:
(1) 1:8～12 in mass ratio, join expansible black lead in dioxane, under agitation condition, mix, and obtain suspending liquid A;
(2) phosphorus oxychloride of rectifying and dioxane are hybridly prepared into solution B, in mass ratio, phosphorus oxychloride and dioxane are 1:8～12, and the expansible black lead in phosphorus oxychloride and step (1) is 1:2～2:5; Solution B is joined in suspending liquid A, obtain mixed solution C, under temperature is 40～60 ℃, nitrogen protection condition, react 0.5～2 hour, obtain reaction solution D;
(3) polyvalent alcohol and catalyzer anhydrous stannous chloride are joined in reaction solution D, in molar ratio, the ratio of the phosphorus oxychloride in polyvalent alcohol and step (2) is 1:1～2:1, in mass ratio, the ratio of catalyzer anhydrous stannous chloride and polyvalent alcohol is 1:500～800, in temperature, be to react 3～5 hours under the condition of 50～70 ℃, obtain reaction solution E;
(4) by 1,3,5-three-glycidyl-S-triazinetrione joins in reaction solution E, in molar ratio, 1, the ratio of the polyvalent alcohol in 3,5-three-glycidyl-S-triazinetrione and step (3) is 1:1～2:1, is to react 8～15 hours under the condition of 80～100 ℃ in temperature, again after suction filtration, with dioxane and ethanol, wash respectively, dry, obtain compound expanding fire retardant;
(5) by thermosetting resin and compound expanding fire retardant in mass ratio 95:5～80:20 under the melt temperature condition of resin, mix, obtain a kind of compound expanding fire retardant modified heat convertible resin.
The granularity of described expansible black lead is 30～400 orders.
Described polyvalent alcohol is tetramethylolmethane, ethylene glycol, or its combination.
Described thermosetting resin is self heat-setting resin, or self can not be subject to the resin of thermofixation and the resin system that solidifying agent forms.
A kind of compound expanding fire retardant modified heat convertible resin obtaining by above-mentioned preparation method.
Compared with prior art, the beneficial effect that the present invention obtains is: the present invention is with compound expanding fire retardant modified heat convertible resin, because this compound expanding fire retardant be take expansible black lead as inorganic phase, phosphorous organic expander type fire retardant is coated on expansible black lead surface in the mode of chemical bonding, therefore when being heated and burn, can form finer and close protective layer, reach excellent hot oxygen shielding effect, thereby give thermotolerance and the flame retardant resistance of modified resin excellence; Meanwhile, this compound expanding fire retardant, with a large amount of hydroxyls and epoxide group, has guaranteed to have good bonding force and good dispersion between this fire retardant and macromolecular material, thereby can under lower content, obtain good thermotolerance and flame retardant effect; Therefore, the cured article of prepared modified heat convertible resin has outstanding resistance toheat and flame retardant properties.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the compound expanding fire retardant that provides of 1,3,5-three-glycidyl-S-triazinetrione, expansible black lead and the embodiment of the present invention 1;
Fig. 2 is the X-ray diffraction spectrogram of the compound expanding fire retardant that provides of expansible black lead and the embodiment of the present invention 1;
Fig. 3 is the Raman spectrogram of the compound expanding fire retardant that provides of expansible black lead and the embodiment of the present invention 1
Fig. 4 is electron scanning micrograph and the distribution diagram of element of the compound expanding fire retardant that provides of the embodiment of the present invention 1;
The cured article of the Modified by Expandable Graphite cyanate ester resin that the bisphenol A cyanate ester resin cured article that Fig. 5 is the compound expanding fire retardant modified cyanic acid ester resin cured article that provides of the embodiment of the present invention 2,3,4 and 5, comparative example 1 provides and comparative example 2 provide under nitrogen atmosphere and temperature rise rate be thermal weight loss (TG) graphic representation of 10 ℃/min;
The limiting oxygen index(LOI) column comparison diagram of the Modified by Expandable Graphite ethylene rhodanate resin curing thing that the bisphenol A cyanate ester resin cured article that Fig. 6 is the compound expanding fire retardant modified cyanic acid ester resin cured article that provides of the embodiment of the present invention 2,3,4 and 5, comparative example 1 provides and comparative example 2 provide;
The electron scanning micrograph of the carbon residue after the Modified by Expandable Graphite ethylene rhodanate resin curing thing burning that the bisphenol A cyanate ester resin cured article that Fig. 7 is the compound expanding fire retardant modified cyanic acid ester resin cured article that provides of the embodiment of the present invention 2, comparative example 1 provides and comparative example 2 provide.
Embodiment
Below in conjunction with drawings and Examples, the technical scheme that invention is adopted is further elaborated.
Embodiment 1
1, the preparation of compound expanding fire retardant
2.58g phosphorus oxychloride is joined in 25.8g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 40 ℃, under nitrogen protection, reacts 2 hours, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:1,2.29g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0046g anhydrous stannous chloride; Be warmed up to 60 ℃ of reactions 4 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:1, by 1,3 of 5.63g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 80 ℃ of reactions 15 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 4 times simultaneously, at 100 ℃, be dried to constant weight, obtain a kind of compound expanding fire retardant.Its infrared spectra, X-ray diffraction spectrogram, Raman spectrogram, electron scanning micrograph and distribution diagram of element are respectively referring to accompanying drawing 1,2,3 and 4.
Referring to accompanying drawing 1, it is the infrared spectrum of the compound expanding fire retardant that provides of 1,3,5-three-glycidyl-S-triazinetrione, expansible black lead and the present embodiment.Can find out stretching vibration peak (3430 cm of occurred-OH of the spectrogram of expansible black lead
-1) and stretching vibration peak (1203 cm of C-O
-1), chemical reaction is carried out on the surface that exists for expansible black lead of-OH provides possibility.The spectrogram of compound expanding fire retardant is at 1307cm
-1and 860cm
-1the stronger absorption peak and the P (OCH that have occurred respectively P=O key
2) the stretching vibration absorption peak of C, and these are in expansible black lead and 1,3, in the spectrogram of 5-three-glycidyl-S-triazinetrione all less than occurring, show that P=O is incorporated in composite fire retardant by esterification, phosphorus oxychloride is introduced in EG surface and with tetramethylolmethane, esterification has occurred simultaneously.In addition, the spectrogram of compound expanding fire retardant is respectively at 1470 cm
-1with 1640 cm
-1having there is the charateristic avsorption band of 1,3,5-three-glycidyl-S-triazinetrione ring texture in place, illustrates that 1,3,5-three-glycidyl-S-triazinetrione is also keyed to the surface of expansible black lead.
Referring to accompanying drawing 2, it is the X-ray diffraction spectrogram of the compound expanding fire retardant that provides of expansible black lead and the present embodiment.Can find out, (002) of compound expanding fire retardant and (004) diffraction peak than diffraction peak intensity corresponding to expansible black lead a little less than, illustrate that compound expanding fire retardant surface exists organism.Can find out, the diffraction peak that expansible black lead is caused by oxidation 10 ° of left and right has disappeared substantially at compound expanding fire retardant, proves the generation that has chemical reaction in the preparation process of compound expanding fire retardant, and has generated one deck organic substance simultaneously.
Referring to accompanying drawing 3, it is the Raman spectrogram of the compound expanding fire retardant that provides of expansible black lead and the present embodiment.All there are three characteristic peaks in expansible black lead and compound expanding fire retardant, they are near the D peaks 1335 cm-1,1582 cm
-1g peak and 2691 cm
-1near 2D peak.The strength ratio of D/G is often used to characterize order and the integrity of carbon material.The D/G value of compound expanding fire retardant is 0.67, and the D/G value of expansible black lead is 0.28, has proved in compound expanding fire retardant preparation process, the chemical reaction that the surface of expansible black lead has occurred.
Referring to accompanying drawing 4, it is the electron scanning micrograph of the compound expanding fire retardant that provides of the present embodiment, a, b and c figure, and the distribution diagram of element d of c figure arrow indication position figure.D figure is followed successively by the distribution plan of elemental carbon C, nitrogen N, oxygen O, phosphorus P from left to right.Can find out, compound expanding fire retardant top layer is uniform-distribution with phosphorus, nitrogen element, and compound expanding fire retardant top layer is the coating layer that contains phosphorus, N structure.
2, the preparation of compound expanding fire retardant modified cyanic acid ester resin
Take compound expanding fire retardant and 95g bisphenol A cyanate ester that 5g above-mentioned steps obtains, they are uniformly mixed at 80 ℃, obtain a kind of compound expanding fire retardant modified cyanic acid ester resin.
Embodiment 2
1, the preparation of compound expanding fire retardant
2 g phosphorus oxychloride are joined in 20g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 50 ℃, under nitrogen protection, reacts 1 hour, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:1,1.03g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0021g anhydrous stannous chloride; Be warmed up to 70 ℃ of reactions 3 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:1.5, by 1,3 of 5.82g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 90 ℃ of reactions 10 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 4 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified cyanic acid ester resin and cured article thereof
Take compound expanding fire retardant and 95g bisphenol A cyanate ester that 5g above-mentioned steps obtains, by they and 80 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified cyanic acid ester resin.
The compound expanding fire retardant modified cyanic acid ester resin obtaining is poured in the mould of preheating, in 150 ℃ of vacuum defoamations 1 hour, respectively according to 180
oc/2h+200
oc/2h+220
othe technique of C/2h is cured, and the demoulding after naturally cooling obtains the compound expanding fire retardant modified cyanic acid ester resin solidifying.The typical performance of cured resin is respectively referring to accompanying drawing 5,6 and 7.
Embodiment 3
1, the preparation of compound expanding fire retardant
Press the compound expanding fire retardant of embodiment 2 preparation.
2, the preparation of compound expanding fire retardant modified cyanic acid ester resin and cured article thereof
Take the compound expanding fire retardant of 10g and 90g bisphenol A cyanate ester, by they and 80 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified cyanic acid ester resin.
The compound expanding fire retardant modified cyanic acid ester resin obtaining is poured in the mould of preheating, in 150 ℃ of vacuum defoamations 1 hour, respectively according to 180
oc/2h+200
oc/2h+220
othe technique of C/2h is cured, and the demoulding after naturally cooling obtains the compound expanding fire retardant modified cyanic acid ester resin solidifying.The typical performance of cured resin is respectively referring to accompanying drawing 5,6 and 7.
Embodiment 4
1, the preparation of compound expanding fire retardant
Press the compound expanding fire retardant of embodiment 2 preparation.
2, the preparation of compound expanding fire retardant modified cyanic acid ester resin and cured article thereof
Take compound expanding fire retardant and 85g bisphenol A cyanate ester that 15g above-mentioned steps obtains, by they and 80 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified cyanic acid ester resin.
The compound expanding fire retardant modified cyanic acid ester resin obtaining is poured in the mould of preheating, in 150 ℃ of vacuum defoamations 1 hour, respectively according to 180
oc/2h+200
oc/2h+220
othe technique of C/2h is cured, and the demoulding after naturally cooling obtains the compound expanding fire retardant modified cyanic acid ester resin solidifying.The typical performance of cured resin is respectively referring to accompanying drawing 5,6 and 7.
Embodiment 5
1, the preparation of compound expanding fire retardant
Press the compound expanding fire retardant of embodiment 2 preparation.
2, the preparation of compound expanding fire retardant modified cyanic acid ester resin and cured article thereof
Take compound expanding fire retardant and 80g bisphenol A cyanate ester that 20g above-mentioned steps obtains, by they and 80 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified cyanic acid ester resin.
The compound expanding fire retardant modified cyanic acid ester resin obtaining is poured in the mould of preheating, in 150 ℃ of vacuum defoamations 1 hour, respectively according to 180
oc/2h+200
oc/2h+220
othe technique of C/2h is cured, and the demoulding after naturally cooling obtains the compound expanding fire retardant modified cyanic acid ester resin solidifying.The typical performance of cured resin is respectively referring to accompanying drawing 5,6 and 7.
Comparative example 1, the preparation of CE resin cured matter: 100g bisphenol A cyanate ester is stirred 15 minutes under 80 ℃ of conditions, the cyanate of thawing is poured in the mould of preheating, in 150 ℃ of vacuum defoamations 1 hour, according to the technique of 180 ℃/2h+200 ℃/2h+220 ℃/2h, be cured again, the demoulding after naturally cooling, obtains curing cyanate ester resin.The typical performance of cured resin is respectively referring to accompanying drawing 5,6 and 7.
Comparative example 2, the preparation of Modified by Expandable Graphite ethylene rhodanate resin curing thing: 100 order expansible black leads and 95g bisphenol A cyanate ester by 5g, they are uniformly mixed to 15 minutes at 80 ℃, obtain prepolymer.Prepolymer is poured in the mould of preheating, in 150 ℃ of vacuum defoamations 1 hour, then according to the technique of 180 ℃/2h+200 ℃/2h+220 ℃/2h, be cured respectively, the demoulding after naturally cooling, obtains curing Modified by Expandable Graphite cyanate ester resin.The typical performance of cured resin is respectively referring to accompanying drawing 5,6 and 7.
Referring to accompanying drawing 5, the Modified by Expandable Graphite ethylene rhodanate resin curing thing that the bisphenol A cyanate ester resin cured article that it is the compound expanding fire retardant modified cyanic acid ester resin cured article that provides of the embodiment of the present invention 2,3,4 and 5, comparative example 1 provides and comparative example 2 provide under nitrogen atmosphere and temperature rise rate be thermal weight loss (TG) curve of 10 ℃/min, its representative data is referring to table 1.By contrast, can find, (1), along with the increase of flame retardant agent content, the initial heat decomposition temperature of the modified resin cured article that embodiment 2,3,4 and 5 provides reduces gradually; The analog value of the bisphenol A cyanate ester cured article that the initial heat decomposition temperature of the modified resin cured article of embodiment 5 and comparative example 1 provide remains basically stable, and the initial heat decomposition temperature of the modified resin cured article of embodiment 2～4 is all higher than the analog value of the bisphenol A cyanate ester cured article of comparative example 1.(2) content of the fire retardant using in the compound expanding fire retardant modified cyanic acid ester resin cured article that the Modified by Expandable Graphite ethylene rhodanate resin curing thing that comparative example 2 provides provides with embodiment 2 is identical, but the initial heat decomposition temperature of the prepared modified resin cured article of embodiment 2, far above the prepared modified resin cured article of comparative example 2, illustrates that the former has higher thermostability.(3) the Modified by Expandable Graphite ethylene rhodanate resin curing phase ratio that the bisphenol A cyanate ester resin cured article that comparative example 1 provides and comparative example 2 provide, the prepared modified cyanic acid ester resin cured article of embodiment 2～5 has higher high temperature carbon yield.Above data have all proved that compound expanding fire retardant modified resin provided by the invention has significant advantage.
Table 1
| ? | Comparative example 1 | Comparative example 2 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Initial decomposition temperature (℃) | 326.3 | 347.2 | 378.6 | 341.9 | 330.2 | 323.4 |
| Carbon yield at 700 ℃ (wt%) | 31.5 | 34.1 | 36.9 | 38.3 | 40.1 | 44.3 |
Referring to accompanying drawing 6, it is the compound expanding fire retardant modified cyanic acid ester resin cured article that provides of the embodiment of the present invention 2,3,4 and 5, the limiting oxygen index(LOI) column comparison diagram of the Modified by Expandable Graphite ethylene rhodanate resin curing thing that provides of bisphenol A cyanate ester resin cured article that comparative example 1 provides and comparative example 2.Can find, the limiting oxygen index(LOI) of the compound expanding fire retardant modified cyanic acid ester resin cured article that embodiment 2～5 provides is significantly higher than the analog value of curing bisphenol A cyanate ester (comparative example 1) and Modified by Expandable Graphite ethylene rhodanate resin curing thing (comparative example 2), shows that compound expanding fire retardant modified cyanic acid ester resin provided by the invention has more excellent flame retardant resistance.
Referring to accompanying drawing 7, the electron scanning micrograph of the carbon residue after the Modified by Expandable Graphite ethylene rhodanate resin curing thing burning that the bisphenol A cyanate ester resin cured article that it is the compound expanding fire retardant modified cyanic acid ester resin cured article that provides of the embodiment of the present invention 2, comparative example 1 provides and comparative example 2 provide.Can find out; the carbon residue of the compound expanding fire retardant modified cyanic acid ester resin cured article that embodiment 2 provides (c and f figure) has formed more fine and close protective layer, and the rear carbon residue of Modified by Expandable Graphite ethylene rhodanate resin curing thing burning (b and e scheme) that after the burning of the bisphenol A cyanate ester resin cured article that comparative example 1 provides, carbon residue (a and d figure) and comparative example 2 provide is comparatively loose.General fine and close protective layer can play good heat shield effect, thereby gives the flame retardant resistance that resin is good.
Embodiment 6
1, the preparation of compound expanding fire retardant
5g 320 order expansible black leads and 60g dioxane are added in there-necked flask, be uniformly mixed, obtain the suspending liquid A of expansible black lead;
1.85g phosphorus oxychloride is joined in 18.5g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 50 ℃, under nitrogen protection, reacts 2 hours, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:1,1.64g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0033g anhydrous stannous chloride; Be warmed up to 60 ℃ of reactions 2 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:2, by 1,3 of 7.17g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 80 ℃ of reactions 15 hours;
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 4 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified cyanic acid ester resin
Take compound expanding fire retardant and 53g bisphenol A cyanate ester and 40g dicyclopentadiene type ethylene rhodanate that 7g above-mentioned steps obtains, they are uniformly mixed at 100 ℃, obtain a kind of compound expanding fire retardant modified cyanic acid ester resin.
Embodiment 7
1, the preparation of compound expanding fire retardant
2.58g phosphorus oxychloride is joined in 25.8g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 60 ℃, under nitrogen protection, reacts 0.5 hour, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:1.5,3.87g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0077g anhydrous stannous chloride; Be warmed up to 70 ℃ of reactions 3 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:1, by 1,3 of 8.45g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 100 ℃ of reactions 8 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 3 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified epoxy resin composite
Take compound expanding fire retardant and 90g epoxy resin E51 that 10g above-mentioned steps obtains, by they and 80 ℃, be uniformly mixed, add 10g curing agent ethylene diamine, stir, obtain a kind of compound expanding fire retardant modified epoxy resin composite.
Embodiment 8
1, the preparation of compound expanding fire retardant
6.5g 80 order expansible black leads and 52g dioxane are added in there-necked flask, be uniformly mixed, obtain the suspending liquid A of expansible black lead;
2.58g phosphorus oxychloride is joined in 20.6g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 40 ℃, under nitrogen protection, reacts 2 hours, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:1,2.29g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0046g anhydrous stannous chloride; Be warmed up to 60 ℃ of reactions 4 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:1, by 1,3 of 5.63g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 80 ℃ of reactions 15 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 4 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified cyanic acid ester/epoxy resin
Take compound expanding fire retardant that 10g above-mentioned steps obtains and 50g bisphenol A cyanate ester, 10g epoxy resin E51, by they and 80 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified cyanic acid ester/epoxy resin.
Embodiment 9
1, the preparation of compound expanding fire retardant
2.58g phosphorus oxychloride is joined in 25.8g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 50 ℃, under nitrogen protection, reacts 1 hour, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:2,5.16g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0103g anhydrous stannous chloride; Be warmed up to 70 ℃ of reactions 3 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:2, by 1,3 of 22.53g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 80 ℃ of reactions 15 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 5 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified bismaleimide/cyanate ester resin
Take compound expanding fire retardant and 50g N that 5g above-mentioned steps obtains, N '-4,4 '-diphenyl methane dimaleimide (BDM), 30g bisphenol A cyanate ester, by at they and 110 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified bismaleimide/cyanate ester resin.
1, the preparation of compound expanding fire retardant
2.58g phosphorus oxychloride is joined in 25.8g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 50 ℃, under nitrogen protection, reacts 1 hour, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and ethylene glycol mol ratio, be 1:2,1.50g ethylene glycol is joined in above-mentioned reaction solution D, and add 0.0019g anhydrous stannous chloride; Be warmed up to 60 ℃ of reactions 4 hours, obtain reaction solution E.Press ethylene glycol and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:1, by 1,3 of 5.63g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 90 ℃ of reactions 10 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 3 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified cyanic acid ester/epoxy resin
Take compound expanding fire retardant that 15g above-mentioned steps obtains and 40g bisphenol A cyanate ester and 20g dicyclopentadiene type ethylene rhodanate, 15g epoxy resin E51, by at they and 100 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified cyanic acid ester/epoxy resin.
Embodiment 11
1, the preparation of compound expanding fire retardant
5g 320 order expansible black leads and 50g dioxane are added in there-necked flask, be uniformly mixed, obtain the suspending liquid A of expansible black lead;
1.85g phosphorus oxychloride is joined in 18.5g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 50 ℃, under nitrogen protection, reacts 2 hours, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:1,1.64g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0033g anhydrous stannous chloride; Be warmed up to 60 ℃ of reactions 2 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:2, by 1,3 of 7.17g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 80 ℃ of reactions 15 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 4 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified cyanic acid ester/bimaleimide resin
Take compound expanding fire retardant that 9g above-mentioned steps obtains and 50g dicyclopentadiene type ethylene rhodanate, 41g N, N'-(4,4'-methylenediphenyl) bismaleimides, by at they and 120 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified cyanic acid ester/bimaleimide resin.
Embodiment 12
1, the preparation of compound expanding fire retardant
6.5g 80 order expansible black leads and 52g dioxane are added in there-necked flask, be uniformly mixed, obtain the suspending liquid A of expansible black lead;
2.58g phosphorus oxychloride is joined in 20.6g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 40 ℃, under nitrogen protection, reacts 2 hours, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:1,2.29g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0033g anhydrous stannous chloride; Be warmed up to 70 ℃ of reactions 3 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:1, by 1,3 of 5.63g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 80 ℃ of reactions 15 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 4 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified bismaleimide resin
53g N, N'-(4,4'-methylenediphenyl) the adjacent diallyl bisphenol of bismaleimides and 40g is after 135 ℃ of pre-polymerization 30min, take the compound expanding fire retardant that 7g above-mentioned steps obtains, they are uniformly mixed at 120 ℃, obtain compound expanding fire retardant modified bismaleimide resin.
Embodiment 13
1, the preparation of compound expanding fire retardant
2.58g phosphorus oxychloride is joined in 25.8g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 50 ℃, under nitrogen protection, reacts 1 hour, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and ethylene glycol mol ratio, be 1:2,1.50g ethylene glycol is joined in above-mentioned reaction solution D, and add 0.0030g anhydrous stannous chloride; Be warmed up to 60 ℃ of reactions 4 hours, obtain reaction solution E.Press ethylene glycol and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:1, by 1,3 of 5.63g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 90 ℃ of reactions 10 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 3 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified epoxy
Take compound expanding fire retardant and 85g epoxy resin E51 that 15g above-mentioned steps obtains, by they and 80 ℃, be uniformly mixed, add 20g curing agent dicyandiamide, stir, obtain a kind of compound expanding fire retardant modified epoxy.
Embodiment 14
1, the preparation of compound expanding fire retardant
2.58g phosphorus oxychloride is joined in 25.8g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 50 ℃, under nitrogen protection, reacts 1 hour, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and ethylene glycol and tetramethylolmethane mol ratio, be 1:1:1,0.75g ethylene glycol and 2.29g tetramethylolmethane joined in above-mentioned reaction solution D, and add 0.0061g anhydrous stannous chloride; Be warmed up to 70 ℃ of reactions 4 hours, obtain reaction solution E.Press tetramethylolmethane and ethylene glycol and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:1:2, by 1,3 of 5.63g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 80 ℃ of reactions 10 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 4 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified bismaleimide resin
58g N, N'-(4,4'-methylenediphenyl) the adjacent diallyl bisphenol of bismaleimides and 45g is after 135 ℃ of pre-polymerization 30min, take the compound expanding fire retardant that 20g above-mentioned steps obtains, they are uniformly mixed at 120 ℃, obtain compound expanding fire retardant modified bismaleimide.
1, the preparation of compound expanding fire retardant
3.7g 320 order expansible black leads and 29.6g dioxane are added in there-necked flask, be uniformly mixed, obtain the suspending liquid A of expansible black lead;
1.85g phosphorus oxychloride is joined in 22.2g dioxane, be mixed with solution B.Solution B is joined in suspending liquid A, obtain mixed solution C; Mixed solution C is heated to 50 ℃, under nitrogen protection, reacts 2 hours, obtained generating the reaction solution D of the expansible black lead of phosphinylidyne chlorination;
By phosphorus oxychloride and tetramethylolmethane mol ratio, be 1:1,1.64g tetramethylolmethane is joined in above-mentioned reaction solution D, and add 0.0033g anhydrous stannous chloride; Be warmed up to 60 ℃ of reactions 2 hours, obtain reaction solution E.Press tetramethylolmethane and 1,3,5-three-glycidyl-S-triazinetrione mol ratio is 1:2, by 1,3 of 7.17g, 5-three-glycidyl-S-triazinetrione joins in reaction solution E, is warmed up to 80 ℃ of reactions 15 hours.
After reaction finishes, to reaction solution suction filtration, use respectively dioxane, washing with alcohol sample 4 times simultaneously, at 100 ℃, be dried to constant weight, obtain compound expanding fire retardant.
2, the preparation of compound expanding fire retardant modified cyanic acid ester/dimaleimide/epoxy resin
Take compound expanding fire retardant and 52g N that 10g above-mentioned steps obtains, a N-penylene bismaleimides, 35g bisphenol A cyanate and 13g epoxy resin E44, by at they and 110 ℃, be uniformly mixed, obtain a kind of compound expanding fire retardant modified cyanic acid ester/dimaleimide/epoxy resin.
Claims (4)
1. a preparation method for compound expanding fire retardant modified heat convertible resin, is characterized in that comprising the steps:
(1) 1:8～12 in mass ratio, join expansible black lead in dioxane, under agitation condition, mix, and obtain suspending liquid A;
(2) phosphorus oxychloride of rectifying and dioxane are hybridly prepared into solution B, in mass ratio, phosphorus oxychloride and dioxane are 1:8～12, and the expansible black lead in phosphorus oxychloride and step (1) is 1:2～2:5; Solution B is joined in suspending liquid A, obtain mixed solution C, under temperature is 40～60 ℃, nitrogen protection condition, react 0.5～2 hour, obtain reaction solution D;
(3) polyvalent alcohol and catalyzer anhydrous stannous chloride are joined in reaction solution D, in molar ratio, the ratio of the phosphorus oxychloride in polyvalent alcohol and step (2) is 1:1～2:1, in mass ratio, the ratio of catalyzer anhydrous stannous chloride and polyvalent alcohol is 1:500～800, in temperature, be to react 3～5 hours under the condition of 50～70 ℃, obtain reaction solution E;
(4) by 1,3,5-three-glycidyl-S-triazinetrione joins in reaction solution E, in molar ratio, 1, the ratio of the polyvalent alcohol in 3,5-three-glycidyl-S-triazinetrione and step (3) is 1:1～2:1, is to react 8～15 hours under the condition of 80～100 ℃ in temperature, again after suction filtration, with dioxane and ethanol, wash respectively, dry, obtain compound expanding fire retardant;
(5) by thermosetting resin and compound expanding fire retardant in mass ratio 95:5～80:20 under the melt temperature condition of resin, mix, obtain a kind of compound expanding fire retardant modified heat convertible resin;
Described thermosetting resin is not for self being subject to the resin of thermofixation and the resin system that solidifying agent forms.
2. the preparation method of a kind of compound expanding fire retardant modified heat convertible resin according to claim 1, is characterized in that: the granularity of described expansible black lead is 30～400 orders.
3. the preparation method of a kind of compound expanding fire retardant modified heat convertible resin according to claim 1, is characterized in that: described polyvalent alcohol is tetramethylolmethane ethylene glycol, or its combination.
4. the compound expanding fire retardant modified heat convertible resin obtaining by claim 1 preparation method.
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