CN100526351C - Heat convertible resin composition and its preparing process - Google Patents
Heat convertible resin composition and its preparing process Download PDFInfo
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- CN100526351C CN100526351C CNB200610089665XA CN200610089665A CN100526351C CN 100526351 C CN100526351 C CN 100526351C CN B200610089665X A CNB200610089665X A CN B200610089665XA CN 200610089665 A CN200610089665 A CN 200610089665A CN 100526351 C CN100526351 C CN 100526351C
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Abstract
The invention discloses a thermosetting resin combination and a preparation method of the thermosetting resin combination. The thermosetting resin combination is prepared by prepolymerization reaction between Claisen rearrangement allylated novolac resins whose weight percentage is of 66 to 90 percent and bismaleimide monomers whose weight percentage is of 10 to 34 percents in the temperature of 100 to 150 DEG C. The Claisen rearrangement allyl novolac resin is made through a Claisen rearrangement reaction of allyl etherified novolac resins. The bismaleimide monomers are provided with a formula I structure, wherein, R1 and R2 are H; R is (see above graph). The invention is not only in high glass transition temperature, but also in fine resistance to heat deterioration performance. Fiber reinforced composites of the invention has high temperature strength/modulus retention, which can be used for preparing high temperature resistant composites that is used temporarily under the temperature of 350 DEG C, and can be applied widely in manufacturing the high temperature resistant composites such as matrix resins for missile radomes in aerospace industry.
Description
Technical field
The present invention relates to a kind of compositions of thermosetting resin and preparation method thereof.
Background technology
Fire resistant resin is widely used in fields such as Aeronautics and Astronautics, electronics, machinery, plays an important role in the Human's production life.Generally speaking, the resistance to elevated temperatures main path that improves resin mainly contains two kinds: the one, and the content by increasing intramolecular high temperature resistant group such as phenyl ring etc., and avoid of the existence of easy decomposition texture as long aliphatic chain, ehter bond etc.; Another is the cross-linking density that improves resin.Traditional structured material contains a large amount of aromatic structures with fire resistant resin such as polyimide, polybenzimidazole equimolecular, itself is also by forming trapezoid structure crosslinking curing, when reaching resistance to elevated temperatures, but drawbacks such as processing difficulties, cost raising have also been brought.Since the nineties, novel fire resistant resins such as poly-aryne have progressively entered practical field, do not discharge small molecules, temperature resistant grade advantages of higher in the solidification process though these resins have, that they also exist is poor, with high costs such as combining with the fortifying fibre interface, solidification process is not easy problems such as control.In addition, in some special Application Areas, as the missile-radars radome etc., the requirement on machining accuracy height, pneumatic high-temperature duration is short, and is disposable use.Therefore, the fire resistant resin of anti-short time high temperature, low cost, easily processing promptly can satisfy the service requirements in these fields.
In the past few decades, utilize Ene reaction and Diels-Alder prepared in reaction one class addition-curable, the research of fire resistant resin cheaply all has expansion at home and abroad, there is the Beijing Aeronautics Research Inst in domestic research unit, Northwestern Polytechnical University and East China University of Science etc., these units are at the diallyl dihydroxyphenyl propane, diallyl etherificate dihydroxyphenyl propane and allyl etherization resol, allyl etherization novel phenolic resin etc. has launched big quantity research with the system of bismaleimides blend, at present, this resinoid has obtained application in dual-use field.
[Journal of applied polymer science such as Yao Yuan, 2005,443] disclose the allyl etherization lacquer resins of a kind of high allylization (allylation degree 〉=100%), itself and the pre-polymerization at a certain temperature of a certain amount of bismaleimide amine monomers have been prepared a kind of blending resin of transparent and homogeneous.This resin system has good building-up properties, is suitable for the RTM moulding process; And resin cured matter has very high second-order transition temperature, and the use temperature in short-term of its matrix material is higher than 350 ℃.But the too high allylation degree of this resin system has reduced the polarity of resin, thereby causes the reduction of resin and fortifying fibre interfacial combined function in the matrix material, and then has influenced the mechanical property of matrix material.
Summary of the invention
The purpose of this invention is to provide a kind of resistant to elevated temperatures compositions of thermosetting resin and preparation method thereof.
Compositions of thermosetting resin provided by the present invention is to be that the allylation lacquer resins reset of 66-90% Claisen and weight percent are that 10-34% bismaleimide amine monomers prepares at 100-150 ℃ of following prepolymerization reactions with weight percent;
The allylation lacquer resins that described Claisen resets makes the allyl etherization lacquer resins by the Claisen rearrangement reaction;
Described bismaleimide amine monomers has formula I structure,
Wherein, R
1, R
2Be H; R is
Or
Preferably, the temperature of Claisen rearrangement reaction is 180～200 ℃, and the reaction times is 2-6h.
The method of used allyl etherization lacquer resins reference [Journal of applied polymerscience, 2005,443] is synthetic, perhaps preparation as follows:
1) phenol is mixed with formaldehyde, Paraformaldehyde 96 aldehyde 1: 0.4 in molar ratio～0.9, add oxalic acid at 25～65 ℃, make lacquer resins 65～95 ℃ of polycondensations, its number-average molecular weight is 450～700;
2) potassium hydroxide is mixed with the butanol solution of above-mentioned lacquer resins, wherein the phenolic hydroxyl group mol ratio in potassium hydroxide and the lacquer resins is 0.90～1.30: 1, drip chlorallylene then and make the allyl etherization lacquer resins, chlorallylene and potassium hydroxide mol ratio are 1.05～1.10: 1.The allyl etherization lacquer resins allylation degree that makes is 90～125%.
The present invention makes to produce phenolic hydroxyl group in the resin structure to strengthen the polarity of resin by with allyl etherization linear phenolic resin process Claisen rearrangement reaction, then resin and the pre-polymerization of bismaleimide amine monomers is obtained resin combination.Because the resin system polar increases, overcome the defective of resin and fiber interface bonding properties difference, so matrix material shows more outstanding mechanical property.
Good and the thermo-oxidative stability of high temperature resistant thermosetting resin combination stability in storage of the present invention has the favorable manufacturability energy, can compression molding.The second-order transition temperature of casting resin is more than 400 ℃, adopt the quartz fabric matrix material of high temperature resistant thermosetting resin combination preparation of the present invention, according to DqES80-98 standard testing matrix material mechanical behavior under high temperature, its matrix material has good bending and interlaminar shear strength at 25 ℃ and 300 ℃.
Compositions of thermosetting resin of the present invention not only has very high second-order transition temperature, has good resistant to thermal aging performance simultaneously, its fibre reinforced composites have higher high temperature strength/modulus conservation rate, can be used for preparing the high temperature resistant composite of under 350 ℃, using in short-term, as the high temperature material in the aerospace industry, the missile-radars radome is with matrix resin etc.
Embodiment
Embodiment 1,
One, the allyl group lacquer resins of preparation rearrangement
1, preparation allyl etherization lacquer resins
Phenol 80g and formaldehyde (37% aqueous solution) 60.9g are added in the reaction flask.Under agitation be warming up to 65 ℃, add oxalic acid 0.484g.Continue to be warming up to 95 ℃, under this temperature, react 180min.Reaction finishes the back and is washed till PH=6.5 with deionized water.Obtain lacquer resins behind the decompression dehydration, its number-average molecular weight is 450.
Above-mentioned lacquer resins 35g is added in the reaction flask, and add propyl carbinol 49g.Heat temperature raising also starts stirring, and temperature rises to about 70 ℃.Treat that it dissolves the back fully and adds potassium hydroxide 26g, after the potassium hydroxide dissolving, be incubated 1 hour, system is cooled to 45 ℃ then.In 60min, slowly add chlorallylene 38g.Be warming up to 80 ℃, under this temperature, react 6h.Filter desalination, with the deionized water wash crude product of heating.Water and propyl carbinol are fallen in underpressure distillation, get the allyl etherization lacquer resins, and its allylation degree is 90-125%.
2, the allyl group lacquer resins of preparation rearrangement
Above-mentioned allyl etherization lacquer resins 50g is joined in the reaction flask, at N
2The protection under be warming up to 200 ℃, and under this temperature stirring reaction 6h, be cooled to 150 ℃ then resin poured out, the allyl group lacquer resins after promptly obtaining resetting.
Two, preparation compositions of thermosetting resin
Above-mentioned allylation resol 30.7g is added in the reaction flask, be warming up to 130 ℃, under agitation in 5min, add 4,4 '-diaminodiphenylmethane bismaleimide amine monomers 12.30g.The molar ratio 100:30 of allyl group and dimaleoyl imino in the maintenance blending resin.Two kinds of components are carried out prepolymerization up to the system transparent and homogeneous under this temperature, be incubated discharging in 5 minutes then, promptly obtain resin combination R-BMAN (100:30) transparent, homogeneous.
In contrast, not through the allyl etherization lacquer resins and 4 of rearrangement, 4 '-diphenyl methane dimaleimide carries out prepolymerization according to identical method, obtains control resin composition BMAN (100:30) with step 2 gained.
Characterize with the curing action of differential calorimetric scanner (DSC) to resin combination, test atmosphere is N
2, temperature rise rate is got 10 ℃/min.The result shows that the curing reaction of resin combination occurs between 200-300 ℃.
With thermogravimetic analysis (TGA) (TGA) and dynamic mechanically mechanical property (DMA) analysis the resistance toheat of resin combination is estimated: adopt 5% weightless temperature of TGA and 900 ℃ residual heavy sign resistance toheat, Tan (δ) peak value of employing DMA characterizes the second-order transition temperature of cured resin.After the gained resin combination solidified by 170 ℃ 2 hours+200 ℃ 2 hours+250 ℃ in 6 hours, obtain brown fine and close casting matrix in the electric heating convection oven.The TGA analysis revealed, cured resin at N
25% weightless temperature is 423 ℃ in the atmosphere, and residual heavy in the time of 900 ℃ is 34.2%; And the heat-resisting oxidative stability of cured resin in air atmosphere significantly improves, and 5% weightless temperature has been brought up to 426 ℃ by 360 ℃ before resetting.The second-order transition temperature of DMA analysis revealed resin is higher than 400 ℃.
By mould pressing process resin combination and quartz fabric are made matrix material, gained matrix material specification is 200mm * 200mm * 2mm, and wherein the quartz fabric number of plies is 15 layers, and resin content is about 30%.Condition of cure is 170 ℃/2h+200 ℃/6h+250 ℃/6h+280 ℃/4h.Matrix material is listed in table 1 at room temperature, 300 ℃ of flexural strengths and Young's modulus, this shows that resin composite materials has excellent mechanical property.
The mechanical property of table 1 composition matrix material
Embodiment 2
One, the allyl group lacquer resins of preparation rearrangement
1, preparation allyl etherization lacquer resins
Phenol 80g and Paraformaldehyde 96 22.53g are added in the reaction flask.Under agitation be warming up to 65 ℃, add oxalic acid 0.484g.Continue to be warming up to 95 ℃, under this temperature, react 180min.Reaction finishes the back and is washed till PH=6.5 with deionized water.Obtain lacquer resins behind the decompression dehydration, its number-average molecular weight is 450.
Above-mentioned lacquer resins 35g is added in the reaction flask, and add propyl carbinol 49g.Heat temperature raising also starts stirring, and temperature rises to about 70 ℃.Treat that it dissolves the back fully and adds potassium hydroxide 26g, after the potassium hydroxide dissolving, be incubated 1 hour, system is cooled to 45 ℃ then.In 60min, slowly add chlorallylene 38g.Be warming up to 80 ℃, under this temperature, react 6h.Filter desalination, with the deionized water wash crude product of heating.Water and propyl carbinol are fallen in underpressure distillation, get the allyl etherization lacquer resins, and its allylation degree is 90-125%.
2, the allyl group lacquer resins of preparation rearrangement
Above-mentioned allyl etherization lacquer resins 50g is joined in the reaction flask, at N
2The protection under be warming up to 200 ℃, and under this temperature stirring reaction 4h, be cooled to 150 ℃ then resin poured out, the allyl group lacquer resins after promptly obtaining resetting.
Two, preparation compositions of thermosetting resin
Above-mentioned allylation resol 30.7g is added in the reaction flask, be warming up to 130 ℃, under agitation in 5min, add 4,4 '-diphenyl methane dimaleimide monomer 24.60g.The molar ratio 100:60 of allyl group and dimaleoyl imino in the maintenance blending resin.Two kinds of components are carried out prepolymerization up to the system transparent and homogeneous under this temperature, be incubated discharging in 5 minutes then, promptly obtain resin compound transparent, homogeneous.With this composition no is R-BMAN (100:60).
In contrast, will be not through the allyl etherization lacquer resins and 4 of rearrangement, 4 '-diphenyl methane dimaleimide carries out prepolymerization after the same method, obtains control resin composition BMAN (100:60).
Characterize with the curing action of differential calorimetric scanner (DSC) to the gained resin combination, test atmosphere is N2, and temperature rise rate is got 10 ℃/min.The result shows that the curing reaction of resin combination occurs between 200-300 ℃.
With thermogravimetic analysis (TGA) (TGA) and dynamic mechanically mechanical property (DMA) analysis the resistance toheat of resin combination is estimated: adopt 5% weightless temperature of TGA and 900 ℃ residual heavy sign resistance toheat, Tan (δ) peak value of employing DMA characterizes the second-order transition temperature of cured resin.After the gained resin combination solidified by 170 ℃ 2 hours+200 ℃ 2 hours+250 ℃ in 6 hours, obtain brown fine and close casting matrix in the electric heating convection oven.The TGA analysis revealed, cured resin at N
25% weightless temperature is 426 ℃ in the atmosphere, in the time of 900 ℃ residual heavy be 36.3%; And the heat-resisting oxidative stability of cured resin in air atmosphere significantly improves, and 5% weightless temperature has been brought up to 423 ℃ by 382 ℃ before resetting.The second-order transition temperature of DMA analysis revealed resin is higher than 400 ℃.
By mould pressing process resin combination and quartz fabric are made matrix material, gained matrix material specification is 200mm * 200mm * 2mm, wherein the quartz fabric number of plies is 15 layers, and resin content is about 30%, and condition of cure is 170 ℃/2h+200 ℃/6h+250 ℃/6h+280 ℃/4h.Matrix material is listed in table 2 at room temperature, 300 ℃ of flexural strengths and Young's modulus, this shows that resin composite materials has excellent mechanical property.
The mechanical property of table 2 composition matrix material
Embodiment 3
One, the allyl group lacquer resins of preparation rearrangement
1, preparation allyl etherization lacquer resins
Phenol 80g and formaldehyde (37% aqueous solution) 60.9g are added in the reaction flask.Under agitation be warming up to 65 ℃, add oxalic acid 0.484g.Continue to be warming up to 95 ℃, under this temperature, react 180min.Reaction finishes the back and is washed till PH=6.5 with deionized water.Obtain lacquer resins behind the decompression dehydration, its number-average molecular weight is 450.
Above-mentioned lacquer resins 35g is added in the reaction flask, and add propyl carbinol 49g.Heat temperature raising also starts stirring, and temperature rises to about 70 ℃.Treat that it dissolves the back fully and adds potassium hydroxide 26g, after the potassium hydroxide dissolving, be incubated 1 hour, system is cooled to 45 ℃ then.In 60min, slowly add chlorallylene 38g.Be warming up to 80 ℃, under this temperature, react 6h.Filter desalination, with the deionized water wash crude product of heating.Water and propyl carbinol are fallen in underpressure distillation, get the allyl etherization lacquer resins, and its allylation degree is 90-125%.
2, the allyl group lacquer resins of preparation rearrangement
Above-mentioned allyl etherization lacquer resins 50g is joined in the reaction flask, at N
2The protection under be warming up to 200 ℃, and under this temperature stirring reaction 6h, be cooled to 150 ℃ then resin poured out, the allyl group lacquer resins after promptly obtaining resetting.
Two, preparation compositions of thermosetting resin
Above-mentioned allylation resol 30.7g is added in the reaction flask, be warming up to 130 ℃, under agitation in 5min, add 4,4 '-sulfobenzide bismaleimide amine monomers 13.80g.The molar ratio 100:30 of allyl group and dimaleoyl imino in the maintenance blending resin.Two kinds of components are carried out prepolymerization up to the system transparent and homogeneous under this temperature, be incubated discharging in 5 minutes then, promptly obtain resin combination transparent, homogeneous.With this composition no is R-BMSN (100:30).
In contrast, not through the allyl etherization lacquer resins and 4 of rearrangement, 4 '-diphenyl methane dimaleimide carries out prepolymerization according to identical method, obtains control resin composition BMAN (100:30) with step 2 gained.
Characterize with the curing action of differential calorimetric scanner (DSC) to resin combination, test atmosphere is N
2, temperature rise rate is got 10 ℃/min.The result shows that the curing reaction of resin combination occurs between 200-300 ℃.
With thermogravimetic analysis (TGA) (TGA) and dynamic mechanically mechanical property (DMA) analysis the resistance toheat of resin combination is estimated: adopt 5% weightless temperature of TGA and 900 ℃ residual heavy sign resistance toheat, Tan (δ) peak value of employing DMA characterizes the second-order transition temperature of cured resin.After the gained resin combination solidified by 170 ℃ 2 hours+200 ℃ 2 hours+250 ℃ in 6 hours, obtain brown fine and close casting matrix in the electric heating convection oven.The TGA analysis revealed, cured resin at N
25% weightless temperature is 429 ℃ in the atmosphere, and residual heavy in the time of 900 ℃ is 35.4%; And the heat-resisting oxidative stability of cured resin in air atmosphere significantly improves, and 5% weightless temperature has been brought up to 413 ℃ by 360 ℃ before resetting.The second-order transition temperature of DMA analysis revealed resin is higher than 400 ℃.
By mould pressing process resin combination and quartz fabric are made matrix material, gained matrix material specification is 200mm * 200mm * 2mm, and wherein the quartz fabric number of plies is 15 layers, and resin content is about 30%.Condition of cure is 170 ℃/2h+200 ℃/6h+250 ℃/6h+280 ℃/4h.Matrix material is listed in table 3 at room temperature, 300 ℃ of flexural strengths and Young's modulus, this shows that resin composite materials has excellent mechanical property.
The mechanical property of table 3 composition matrix material
Embodiment 4
One, the allyl group lacquer resins of preparation rearrangement
1, preparation allyl etherization lacquer resins
Phenol 80g and formaldehyde (37% aqueous solution) 60.9g are added in the reaction flask.Under agitation be warming up to 65 ℃, add oxalic acid 0.484g.Continue to be warming up to 95 ℃, under this temperature, react 180min.Reaction finishes the back and is washed till PH=6.5 with deionized water.Obtain lacquer resins behind the decompression dehydration, its number-average molecular weight is 450.
Above-mentioned lacquer resins 35g is added in the reaction flask, and add propyl carbinol 49g.Heat temperature raising also starts stirring, and temperature rises to about 70 ℃.Treat that it dissolves the back fully and adds potassium hydroxide 26g, after the potassium hydroxide dissolving, be incubated 1 hour, system is cooled to 45 ℃ then.In 60min, slowly add chlorallylene 38g.Be warming up to 80 ℃, under this temperature, react 6h.Filter desalination, with the deionized water wash crude product of heating.Water and propyl carbinol are fallen in underpressure distillation, get the allyl etherization lacquer resins, and its allylation degree is 90-125%.
2, the allyl group lacquer resins of preparation rearrangement
Above-mentioned allyl etherization lacquer resins 50g is joined in the reaction flask, at N
2The protection under be warming up to 200 ℃, and under this temperature stirring reaction 6h, be cooled to 150 ℃ then resin poured out, the allyl group lacquer resins after promptly obtaining resetting.
Two, preparation compositions of thermosetting resin
Above-mentioned allylation resol 30.7g is added in the reaction flask, be warming up to 130 ℃, under agitation in 5min, add 4,4 '-phenyl ether bismaleimide amine monomers 12.20g.The molar ratio 100: 30 that keeps allyl group and dimaleoyl imino in the blending resin.Two kinds of components are carried out prepolymerization up to the system transparent and homogeneous under this temperature, be incubated discharging in 5 minutes then, promptly obtain resin combination transparent, homogeneous.With this composition no is R-BMEN (100:30).
In contrast, not through the allyl etherization lacquer resins and 4 of rearrangement, 4 '-diphenyl methane dimaleimide carries out prepolymerization according to identical method, obtains control resin composition BMAN (100:30) with step 2 gained.
Characterize with the curing action of differential calorimetric scanner (DSC) to resin combination, test atmosphere is N
2, temperature rise rate is got 10 ℃/min.The result shows that the curing reaction of resin combination occurs between 200-300 ℃.
With thermogravimetic analysis (TGA) (TGA) and dynamic mechanically mechanical property (DMA) analysis the resistance toheat of resin combination is estimated: adopt 5% weightless temperature of TGA and 900 ℃ residual heavy sign resistance toheat, Tan (δ) peak value of employing DMA characterizes the second-order transition temperature of cured resin.After the gained resin combination solidified by 170 ℃ 2 hours+200 ℃ 2 hours+250 ℃ in 6 hours, obtain brown fine and close casting matrix in the electric heating convection oven.The TGA analysis revealed, cured resin at N
25% weightless temperature is 414 ℃ in the atmosphere, and residual heavy in the time of 900 ℃ is 32.3%; And the heat-resisting oxidative stability of cured resin in air atmosphere significantly improves, and 5% weightless temperature has been brought up to 404 ℃ by 360 ℃ before resetting.The second-order transition temperature of DMA analysis revealed resin is higher than 400 ℃.
By mould pressing process resin combination and quartz fabric are made matrix material, gained matrix material specification is 200mm * 200mm * 2mm, and wherein the quartz fabric number of plies is 15 layers, and resin content is about 30%.Condition of cure is 170 ℃/2h+200 ℃/6h+250 ℃/6h+280 ℃/4h.Matrix material is listed in table 4 at room temperature, 300 ℃ of flexural strengths and Young's modulus, this shows that resin composite materials has excellent mechanical property.
The mechanical property of table 4 composition matrix material
Claims (4)
1, a kind of compositions of thermosetting resin is to be that the allylation lacquer resins reset of 66-90% Claisen and weight percent are that 10-34% bismaleimide amine monomers prepares at 100-150 ℃ of following prepolymerization reactions with weight percent;
The allylation lacquer resins that described Claisen resets makes the allyl etherization lacquer resins by the Claisen rearrangement reaction; Described allyl etherization lacquer resins prepares as follows:
1) phenol is mixed with formaldehyde or Paraformaldehyde 96 1: 0.4 in molar ratio～0.9, add oxalic acid at 25～65 ℃, make lacquer resins 65～95 ℃ of polycondensations, its number-average molecular weight is 450～700;
2) potassium hydroxide is mixed with the butanol solution of above-mentioned lacquer resins, wherein the phenolic hydroxyl group mol ratio in potassium hydroxide and the lacquer resins is 0.90～1.30: 1, drip chlorallylene then and make the allyl etherization lacquer resins, chlorallylene and potassium hydroxide mol ratio are 1.05～1.10: 1;
Described bismaleimide amine monomers has formula I structure,
Wherein, R
1And R
2Be H; R is
Or
2, compositions of thermosetting resin according to claim 1 is characterized in that: the temperature of described Claisen rearrangement reaction is 180-200 ℃, and the reaction times is 2-6h.
3, the preparation method of the described compositions of thermosetting resin of claim 1, with weight percent be the allylation lacquer resins reset of 66-90% Claisen and weight percent be 10-34% bismaleimide amine monomers at 100-150 ℃ of following prepolymerization reactions, prepare described compositions of thermosetting resin;
The allylation lacquer resins that described Claisen resets makes the allyl etherization lacquer resins by the Claisen rearrangement reaction; Described allyl etherization lacquer resins prepares as follows:
1) phenol is mixed with formaldehyde or Paraformaldehyde 96 1: 0.4 in molar ratio～0.9, add oxalic acid at 25～65 ℃, make lacquer resins 65～95 ℃ of polycondensations, its number-average molecular weight is 450～700;
2) potassium hydroxide is mixed with the butanol solution of above-mentioned lacquer resins, wherein the phenolic hydroxyl group mol ratio in potassium hydroxide and the lacquer resins is 0.90～1.30: 1, drip chlorallylene then and make the allyl etherization lacquer resins, chlorallylene and potassium hydroxide mol ratio are 1.05～1.10: 1;
Described bismaleimide amine monomers has formula I structure,
Wherein, R
1And R
2Be H; R is
Or
4, preparation method according to claim 3 is characterized in that: the temperature of described Claisen rearrangement reaction is 180-200 ℃, and the reaction times is 2-6h.
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| CN101538347B (en) * | 2009-02-06 | 2013-11-13 | 上海华谊（集团）公司 | Maleimide copolymer and synthetic method thereof |
| CN101619123B (en) * | 2009-08-14 | 2011-03-16 | 东华大学 | High temperature resistant composite matrix resin and preparation method thereof |
| CN102372832B (en) * | 2010-08-11 | 2013-09-25 | 中国科学院化学研究所 | Phthalonitrile-based etherified phenolic resin and preparation method thereof |
| CN103360557B (en) * | 2013-07-25 | 2015-11-11 | 南京市荣达树脂有限公司 | A kind of modified phenolic resins |
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| CN103396650B (en) * | 2013-07-25 | 2016-04-06 | 南京市荣达树脂有限公司 | A kind of modified alkyd resin based friction material |
| CN103396651A (en) * | 2013-07-25 | 2013-11-20 | 南京市荣达树脂有限公司 | Preparation method of modified phenolic resin-base friction material |
| KR102413139B1 (en) * | 2014-07-01 | 2022-06-27 | 우베 가부시키가이샤 | Allyl ether-modified biphenyl aralkyl novolac resin, allyl-modified biphenyl aralkyl novolac resin, method for producing same and composition using same |
| CN109306044A (en) * | 2017-07-26 | 2019-02-05 | 郑州大学 | A kind of intrinsic flame-retarded resin of low polarity and its preparation method and application |
| CN109306039A (en) * | 2017-07-26 | 2019-02-05 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it |
| CN109306040A (en) * | 2017-07-26 | 2019-02-05 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and the high-frequency circuit board made by it |
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Application publication date: 20080116 Assignee: Jiangsu Fengmang Composite Material S&T Group Co., Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract record no.: 2013320000109 Denomination of invention: Heat convertible resin composition and its preparing process Granted publication date: 20090812 License type: Common License Record date: 20130314 |
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