CN103524691B - Nano-TiO 2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof - Google Patents
Nano-TiO 2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof Download PDFInfo
- Publication number
- CN103524691B CN103524691B CN201310465092.6A CN201310465092A CN103524691B CN 103524691 B CN103524691 B CN 103524691B CN 201310465092 A CN201310465092 A CN 201310465092A CN 103524691 B CN103524691 B CN 103524691B
- Authority
- CN
- China
- Prior art keywords
- tio
- nano
- maleimide
- phenolic aldehyde
- situ reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention overcomes the low deficiency of resol thermotolerance and high-temperature hot residual rate in prior art, provides a kind of nano-TiO
2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof.TiO in compound resin
2content is 0.7% ~ 4.0%, and maleimide content is 5.5% ~ 11.8%, and preparation method is, (1) is first by formaldehyde, nano-TiO
2, silane coupling agent and dispersion agent be uniformly dispersed under ul-trasonic irradiation, adds maleimide and acid catalyst simultaneously, raised temperature also drips the ethanolic soln of phenol, then be warming up to 90 DEG C of insulation reaction, obtains modified phenolic resins prepolymer; (2) be heating and curing on flat vulcanizer and namely obtain in-situ composite.Nanoparticle is evenly dispersed in maleimide phenolic resin matrix more, solidifies without the need to external reinforcement agent, and does not discharge small molecules in solidification process, improves phenolic cure structure, gives the higher thermotolerance of resin and high-temperature hot residual rate.
Description
Technical field
The invention belongs to modified phenolic resins field, particularly relate to a kind of heat resistant phenolic compound resin and preparation method thereof.
Background technology
Resol (PF) abundant raw material source, production technique and equipment are simple, and product size is stablized, and has heat-resisting, fire-retardant, that high temperature Residual carbon is high advantage, is widely used in the fields such as automobile, electrical equipment, casting, electromechanics, aerospace.But the shortcomings such as fragility is large, water-absorbent is high, condensation cured generation small molecules that common PF exists, if and use temperature is more than 200 DEG C, phenolic hydroxyl group and methylene radical are very easily degraded by high-temperature thermal oxidation, thermal weight loss significantly improves, far can not meet the requirement of numerous high-technology field, the resistant to elevated temperatures High Performance Phenolic Resins of development of new is imperative.
Current raising resol thermotolerance and high-temperature hot carbon yield adopt chemical modification approach usually, as by the phenolic hydroxyl group etherificate esterification of resol, heavy metal chelating and strict post cure condition, strengthen hardener dose etc.As Chinese patent CN100365037C discloses a kind of in-situ preparation method of nano SiO 2/boron bakelite resin nano composite material, boron bakelite resin inherently has good thermotolerance, then adds the SiO of rigidity
2, wear resistance, thermo-chemical stability have also been obtained raising, but dissolve, processing characteristics is poor, limits its range of application; Chinese patent CN102181025A discloses the preparation method of a kind of nano silicon and rubber modified synergic resol, although can reach nano-scale dispersion, resin toughness shock strength increases, and resistance toheat declines to some extent; Chinese patent CN102432785A discloses a kind of preparation method of original position dispersion nano polybasic graft modified phenolic resin, although toughness of products, thermal property, rheological etc. are obtained for raising, but use raw material too much, be not easily uniformly dispersed, technological process relative complex.Above patent all needs additional vulkacit H solidifying agent to carry out condensation cured, discharges small molecules in solidification process, and then makes the structure of material occur many micropores and cause material property to decline.
Addition curable resol is a class novel phenolic resins of development in recent years, and owing to adopting addition curing mechanism, solidification process, without the need to adding solidifying agent, can improve phenolic cure structure, gives the thermotolerance that resin is higher.Chemically thermostability and the excellent maleimide amine component of add-on type group that has of chemical resistant properties are introduced in phenolic resin structure, novel addition curable resol can be obtained, foreign literature (Modificationofpolyaralkyl-phenolicresinanditscopolymerwi thbismaleimide.J.Appl.PolymerSci., 1996,59:975-979) the phenol aldehyde modified system of report introducing dimaleoyl imino group has preferably resistance toheat, but the dissolving processing characteristics of this resin is poor.
Summary of the invention
The present invention overcomes the low deficiency of resol thermotolerance and high-temperature hot residual rate in prior art, provides a kind of nano-TiO
2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof.
The technical solution adopted in the present invention is as follows: a kind of nano-TiO
2/ maleimide phenolic aldehyde In-situ reaction resin, wherein TiO
2mass percent is 0.7% ~ 4.0%, and maleimide mass percent is 5.5% ~ 11.8%.
As preferably, described nano-TiO
2tiO in/maleimide phenolic aldehyde In-situ reaction resin
2mass percent is 3.0% ~ 3.3%.
Above-mentioned nano-TiO
2the preparation method of/maleimide phenolic aldehyde In-situ reaction resin, step is as follows,
(1) first by formaldehyde, nano-TiO
2, silane coupling agent and dispersion agent be uniformly dispersed under ul-trasonic irradiation, add maleimide and acid catalyst simultaneously, the ethanolic soln of phenol is dripped wherein after raised temperature to 75 DEG C, again be warming up to 90 DEG C of insulation reaction 4 ~ 12h, underpressure distillation, discharging, is cooled to room temperature, in vacuum drying oven, 50 DEG C of dry 12h, namely obtain the nano-TiO of golden transparent solid
2/ maleimide phenolic aldehyde In-situ reaction resin prepolymer;
(2) prepolymer obtained in step (1) is put into framed, on flat vulcanizer in 250 DEG C, under 1 ~ 20MPa, solidify 1 ~ 5 hour, obtain nano-TiO
2/ maleimide phenolic resin in-situ composite.
Further, described ultrasonication is disperse 10 ~ 40min under 20 ~ 2000kHz ultrasonication.
Further, raw material composition is according to the mass fraction: phenol 10 ~ 60 parts, alcoholic solvent 4 ~ 24 parts, 37% formalin 8 ~ 48 parts; Maleimide 2 ~ 12 parts, acid catalyst 0.5 ~ 3 part, nano-TiO
2: 0.1 ~ 1.5 part; Coupling agent: 0.01 ~ 0.15 part; Dispersion agent: 0.05 ~ 0.75 part.
As preferably, described nano-TiO
2consumption is 5% of phenol quality.
As preferably, described acid catalyst is oxalic acid or hydrochloric acid; Described maleimide is the single maleimide containing unsaturated double-strand, comprises the one in N-hydroxyphenyl-maleimides (HPM), N-phenylmaleimide (N-PMI) or N-carboxyl phenyl maleimide.
Further, described coupling agent is one or more in N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), γ-aminopropyl triethoxysilane (KH550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) or γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570); Described dispersion agent is the one in polyphosphoric acid type, polysilicon acid class, polycarboxylic acid, polyester type or polyether-type hyper-dispersant.
The present invention selects dissolves the good single maleimide of processing characteristics as rigid heat resistant, addition component, with chemical and that thermostability is very high nano titanium oxide for rigid function particle, the higher thermotolerance of resol and high-temperature hot residual rate is imparted by both synergies, and a step fabricated in situ, simplify and shorten production stage, obviously can reduce production cost, in fields such as automobile, space flight and aviation high temperature materials, there is larger practical value and excellent application prospect;
With traditional blended compared with, easily there is the problem of reuniting in effective solution nanoparticle, nanoparticle is evenly dispersed in maleimide phenolic resin matrix more, this In-situ reaction resin adopts the solidification of addition curing mechanism, without the need to external reinforcement agent, do not discharge small molecules in solidification process, the structure of material can not be made to occur micropore, thus improve phenolic cure structure.
Accompanying drawing explanation
Fig. 1 is the TG curve (atmosphere: nitrogen) of the obtained product of embodiment 5, comparative example 1, comparative example 2 and comparative example 3;
Fig. 2 is the stereoscan photograph that embodiment 5 obtains product.
Embodiment
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
Testing method:
Component concentration measuring method in product:
Nano-TiO
2tiO in/N-phenylmaleimide phenolic aldehyde In-situ reaction resin
2content: adopt retort furnace to calcine 2h at 900 DEG C, calcines organic polymer resin clean completely, only remains inorganics TiO
2, poidometer calculates TiO
2the quality percentage of shared sample;
In modified resin, maleimide content measures: adopt the nitrogen content in the sample of the EA2400 II type elemental analyser analytical test of U.S. PerkinElmer company through being separated the unconverted maleimide of removing, through the maleimide content in modified resin of converting to obtain.
Performance test methods:
The resistance toheat of In-situ reaction resin sample and high-temperature residual rate adopt the SDTQ600 type thermogravimetric analyzer test of TG instrument company of the U.S., and test condition is nitrogen protection, rises to 850 DEG C with the temperature rise rate of 20 DEG C/min from 50 DEG C.
Embodiment 1:
Step (1): take 0.1g nano-TiO respectively
2(1% of phenol quality), 8g formaldehyde solution, 0.01g coupling agent KH560,0.05g dispersion agent 598, disperses 20 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, take 2gN-phenyl maleimide and 0.5g oxalic acid, add together in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed, be warming up to 75 DEG C, the solution that the 10g phenol prepared in advance is dissolved in 4g ethanol is dripped with constant pressure funnel, drip 30min, be warming up to 90 DEG C, insulation reaction 4 hours, underpressure distillation, discharging, is cooled to room temperature, obtains nano-TiO
2content is 0.7%(mass percent, lower with), N-PMI content is 11.8%(mass percent, lower with) TiO
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer is put into framed, 250 DEG C, solidify 2 hours on vulcanizing press under 5MPa pressure, obtains nano-TiO
2content to be 0.7%, N-PMI content be 11.8% nano-TiO
2/ N-phenylmaleimide phenolic aldehyde in-situ composite.Performance test is in table 1.
Embodiment 2
Step (1): take 1.2g nano-TiO respectively
2(2% of phenol quality), 48g formaldehyde, 0.12g coupling agent KH560,0.6g dispersion agent 598, disperses 15 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, takes 12gN-phenyl maleimide and 3g oxalic acid, adds in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed together, be warming up to 75 DEG C, drip with constant pressure funnel the solution that the 60g phenol prepared in advance is dissolved in 24g methyl alcohol, drip 30min, be warming up to 90 DEG C, insulation reaction 6 hours, underpressure distillation, discharging, is cooled to room temperature, obtain the nanometer that nanometer content is 1.3%, N-PMI content is the TiO of 11.7%
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer is put into framed, 250 DEG C, solidify 1 hour on vulcanizing press under 10MPa pressure, obtains nano-TiO
2content to be 1.3%, N-PMI content be 11.7% nano-TiO
2/ N-phenylmaleimide phenolic aldehyde in-situ composite.Performance test is in table 1.
Embodiment 3:
Take 0.9g nano-TiO respectively
2(3% of phenol quality), 24g formaldehyde, 0.09g coupling agent KH560,0.45g dispersion agent 598, disperses 30 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, take 6gN-phenyl maleimide and 1.5g oxalic acid, add together in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed, be warming up to 75 DEG C, the solution that the 30g phenol prepared in advance is dissolved in 12g ethanol is dripped with constant pressure funnel, drip 30min, be warming up to 90 DEG C, insulation reaction 8 hours, underpressure distillation, discharging, is cooled to room temperature, obtains nano-TiO
2content to be 2.0%, N-PMI content be 11.5% nano-TiO
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ N-phenylmaleimide resol prepolymer is put into framed, 250 DEG C, solidify 2 hours on vulcanizing press under 5MPa pressure, obtains nano-TiO
2content to be 2.0%, N-PMI content be 11.5% nano-TiO
2/ N-phenylmaleimide phenolic aldehyde in-situ composite.Performance test is in table 1.
Embodiment 4:
Take 0.6g nano-TiO respectively
2(4% of phenol quality), 12g formaldehyde solution, 0.06g coupling agent KH570,0.3g dispersion agent 6300, disperses 40 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, take 3gN-phenyl maleimide and 0.8g oxalic acid, add together in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed, be warming up to 75 DEG C, the solution that the 15g phenol prepared in advance is dissolved in 6g ethanol is dripped with constant pressure funnel, drip 30min, be warming up to 90 DEG C, insulation reaction 8 hours, underpressure distillation, discharging, is cooled to room temperature, obtains nano-TiO
2content to be 2.7%, N-PMI content be 11.4% TiO
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer is put into framed, 250 DEG C, solidify 5 hours on vulcanizing press under 20MPa pressure, obtains nano-TiO
2content to be 2.7%, N-PMI content be 11.4% nano-TiO
2/ N-phenylmaleimide phenolic aldehyde in-situ composite.Performance test is in table 1.
Embodiment 5:
Take 1.0g nano-TiO respectively
2(5% of phenol quality), 16g formaldehyde solution, 0.1g coupling agent KH560,0.5g dispersion agent 598, disperses 30 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, take 4gN-phenyl maleimide and 1g oxalic acid, add together in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed, be warming up to 75 DEG C, the solution that the 20g phenol prepared in advance is dissolved in 8g ethanol is dripped with constant pressure funnel, drip 30min, be warming up to 90 DEG C, be incubated anti-12 hours, underpressure distillation, discharging, is cooled to room temperature, obtains nano-TiO
2content to be 3.0% ~ 3.3%, N-PMI content be 11.3% TiO
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer is put into framed, 250 DEG C, solidify 2 hours on vulcanizing press under 5MPa pressure, obtains nano-TiO
2content to be 3.0% ~ 3.3%, N-PMI content be 11.3% nano-TiO
2/ N-phenylmaleimide phenolic aldehyde in-situ composite.Performance test is in table 1.
Embodiment 6:
Take 1.5g nano-TiO respectively
2(6% of phenol quality), 20g formaldehyde solution, 0.15g coupling agent KH792,0.75g dispersion agent 6300, disperses 30 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, take 5gN-phenyl maleimide and 1.5g oxalic acid, add together in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed, be warming up to 75 DEG C, the solution that the 25g phenol prepared in advance is dissolved in 10g ethanol is dripped with constant pressure funnel, drip 30min, be warming up to 90 DEG C, be incubated anti-10 hours, underpressure distillation, discharging, is cooled to room temperature, obtains nano-TiO
2content to be 4.0%, N-PMI content be 11.1% TiO
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer is put into framed, 250 DEG C, solidify 3 hours on vulcanizing press under 3MPa pressure, obtains nano-TiO
2content to be 4.0%, N-PMI content be 11.1% nano-TiO
2/ N-phenylmaleimide phenolic aldehyde in-situ composite.Performance test is in table 1.
Embodiment 7:
Take 1.5g nano-TiO respectively
2(6% of phenol quality), 20g formaldehyde solution, 0.15g coupling agent KH792,0.75g dispersion agent 6300, disperses 30 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, take 5gN-(4-hydroxy phenyl) maleimide and 1.5g oxalic acid, add together in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed, be warming up to 75 DEG C, the solution that the 25g phenol prepared in advance is dissolved in 10g ethanol is dripped with constant pressure funnel, drip 30min, be warming up to 90 DEG C, be incubated anti-10 hours, underpressure distillation, discharging, is cooled to room temperature, obtains nano-TiO
2content to be 4.0%, HPM content be 11.3% TiO
2/ N-(4-hydroxy phenyl) maleimide phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ N-(4-hydroxy phenyl) maleimide phenolic aldehyde In-situ reaction resin prepolymer is put into framed, 250 DEG C, solidify 3 hours on vulcanizing press under 3MPa pressure, obtains nano-TiO
2content to be 4.0%, HPM content be 11.3% nano-TiO
2/ N-(4-hydroxy phenyl) maleimide phenolic aldehyde in-situ composite.Performance test is in table 1.
Embodiment 8:
Take 1.5g nano-TiO respectively
2(6% of phenol quality), 20g formaldehyde solution, 0.15g coupling agent KH792,0.75g dispersion agent 6300, disperses 30 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, take 2.5gN-phenyl maleimide and 1.5g oxalic acid, add together in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed, be warming up to 75 DEG C, the solution that the 25g phenol prepared in advance is dissolved in 10g ethanol is dripped with constant pressure funnel, drip 30min, be warming up to 90 DEG C, be incubated anti-10 hours, underpressure distillation, discharging, is cooled to room temperature, obtains nano-TiO
2content to be 4.0%, N-PMI content be 5.5% TiO
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ N-phenylmaleimide phenolic aldehyde In-situ reaction resin prepolymer is put into framed, 250 DEG C, solidify 3 hours on vulcanizing press under 3MPa pressure, obtains nano-TiO
2content to be 4.0%, N-PMI content be 5.5% nano-TiO
2/ N-phenylmaleimide phenolic aldehyde in-situ composite.Performance test is in table 1.
Comparative example 1:
TiO is added by embodiment 5
2step is removed, other conditions are with embodiment 5, concrete steps are as follows: step (1): take formaldehyde 16g respectively, N-phenylmaleimide 4g and oxalic acid 1g, add in the four-hole boiling flask that thermometer, agitator, reflux exchanger are housed together, be warming up to 75 DEG C, drip with constant pressure funnel the solution that the 20g phenol prepared in advance is dissolved in 8g ethanol, utilize constant pressure funnel to drip phenol, drip 30min, be warming up to 90 DEG C, insulation reaction 12 hours, underpressure distillation, discharging, be cooled to room temperature, obtain N-phenylmaleimide modified phenolic resins prepolymer.
Step (2): N-phenylmaleimide modified phenolic resins prepolymer step (1) obtained is put into framed, obtains the PPMF resin material that N-PMI content is 12% by 250 DEG C, solidify 2 hours on vulcanizing press under 5MPa pressure.Performance test is in table 1.
Comparative example 2:
Remove adding N-phenylmaleimide step in embodiment 5, other conditions are with embodiment 5, and concrete steps are as follows: take 1g nano-TiO respectively
2(5% of phenol quality), 16g formaldehyde solution, 0.1g coupling agent KH560,0.5g dispersion agent 598, disperses 30 minutes, obtains the nano-TiO of surface modification treatment in single port flask under 20 ~ 2000kHz ultrasonication
2formaldehyde dispersion liquid, take 1g oxalic acid, add together in the four-hole boiling flask that agitator, thermometer and reflux exchanger are housed, be warming up to 75 DEG C, the solution that the 20g phenol prepared in advance is dissolved in 8g ethanol is dripped with constant pressure funnel, drip 30min, be warming up to 90 DEG C, be incubated anti-12 hours, underpressure distillation, discharging, is cooled to room temperature, obtains nano-TiO
2content is the nano-TiO of 4.0%
2/ phenolic aldehyde In-situ reaction resin prepolymer.
Step (2): the nano-TiO that step (1) is obtained
2/ phenolic aldehyde In-situ reaction resin prepolymer is put into framed, 250 DEG C, solidify 2 hours on vulcanizing press under 5MPa pressure, obtains nano-TiO
2content is the nano-TiO of 4.0%
2/ phenolic aldehyde in-situ composite.Performance test is in table 1.
Comparative example 3:
Step (1): take following raw material: phenol 20g; Formaldehyde 16g part; Oxalic acid 1 part.Formaldehyde, phenol, oxalic acid are put into four-hole boiling flask, rises to 95 DEG C, react 4 hours, underpressure distillation, terminate reaction, product puts into vacuum oven 12h(50 DEG C), obtain rose pink transparent solid shape resol.
Step (2): the resol 5g got in step (1) puts into framed, adds 0.5g vulkacit H (resol quality 10%), at 150 DEG C, solidifies 2 hours, obtain pure phenolic resin under 5MPa pressure on vulcanizing press.Performance test is in table 1.
As Fig. 1,2. curve does not add nano-TiO for comparative example 1(
2) addition curable PPMF resin addition curing after TG curve, 393 DEG C of weightlessness are only 5%, hot residual rate when 850 DEG C is 67.2%, and resistance toheat is better than the condensation cured pure phenolic resin of traditional use solidifying agent (curve 4.) and comparative example 2 resin (not adding maleimide) (curve 3.); 3. curve does not add maleimide for comparative example 2() TiO
2modified phenolic resins TG curve, as can be seen from curve 3. in, temperature of initial decomposition is 350 DEG C, and 850 DEG C of residual rates are 51.8%;
1. curve is novel addition curable nano-TiO prepared by embodiment 5
2tG curve after/PPMF resin addition curing, its resistance toheat is obviously better than again its excess-three bar curve, and when 486 DEG C, weightlessness is only 5%, improves 196 DEG C than pure phenolic resin, and the hot residual rate 850 DEG C time is 73.3%, improves 26.8% than pure phenolic resin.
By comparing, visible: being used alone temperature of initial decomposition when N-PMI carries out modified phenolic resins (weightless 5%) is 393 DEG C, 850 DEG C of residual rates are 67.2%, and to be used alone temperature of initial decomposition when nano titanium oxide carries out modified phenolic resins be 350 DEG C, 850 DEG C of residual rates are 51.8%, it is 486 DEG C by the two modified synergic resol temperature of initial decomposition, residual rate is 73.3%, significantly better than being used alone N-PMI and being used alone the effect of simple superposition when nano titanium oxide carries out modification PF, temperature of initial decomposition improves a lot, illustrate that in embodiment 5, N-PMI and titanium dioxide all enter in phenolic aldehyde chain, improve the structure of resol, modified synergic Be very effective.
Nano-TiO as can be seen from Figure 2
2be distributed in maleimide phenolic resin equably, and occur through modification phenolic resin-based pore-free structure.
The resistance toheat of resin obtained by each embodiment of table 1 and high-temperature residual rate performance
Claims (7)
1. a nano-TiO
2/ maleimide phenolic aldehyde In-situ reaction resin, is characterized in that: described nano-TiO
2tiO in/maleimide phenolic aldehyde In-situ reaction resin
2mass percent is 3.0% ~ 3.3%, and maleimide mass percent is 5.5% ~ 11.8%.
2. nano-TiO according to claim 1
2the preparation method of/maleimide phenolic aldehyde In-situ reaction resin, is characterized in that step is as follows:
(1) first by formaldehyde, nano-TiO
2, silane coupling agent and dispersion agent be uniformly dispersed under ul-trasonic irradiation, add maleimide and acid catalyst simultaneously, the ethanolic soln of phenol is dripped wherein after raised temperature to 75 DEG C, again be warming up to 90 DEG C of insulation reaction 4 ~ 12h, underpressure distillation, discharging, is cooled to room temperature, in vacuum drying oven, 50 DEG C of dry 12h, namely obtain the nano-TiO of golden transparent solid
2/ maleimide phenolic aldehyde In-situ reaction resin prepolymer;
(2) prepolymer obtained in step (1) is put into framed, on vulcanizing press in 250 DEG C, under 1 ~ 20MPa, solidify 1 ~ 5 hour, obtain nano-TiO
2/ maleimide phenolic resin in-situ composite.
3. nano-TiO according to claim 2
2the preparation method of/maleimide phenolic aldehyde In-situ reaction resin, is characterized in that: described ul-trasonic irradiation for disperseing 10 ~ 40min under 20 ~ 2000kHz ultrasonication.
4. nano-TiO according to claim 2
2the preparation method of/maleimide phenolic aldehyde In-situ reaction resin, is characterized in that: raw material composition is according to the mass fraction: phenol 10 ~ 60 parts, alcohol solvent 4 ~ 24 parts, 37% formalin 8 ~ 48 parts, maleimide 2 ~ 12 parts, acid catalyst 0.5 ~ 3 part, nano-TiO
2: 0.1 ~ 1.5 part, coupling agent: 0.01 ~ 0.15 part, dispersion agent: 0.05 ~ 0.75 part.
5. nano-TiO according to claim 2
2the preparation method of/maleimide phenolic aldehyde In-situ reaction resin, is characterized in that: described nano-TiO
2consumption is 5% of phenol quality.
6. nano-TiO according to claim 2
2the preparation method of/maleimide phenolic aldehyde In-situ reaction resin, is characterized in that: described acid catalyst is oxalic acid or hydrochloric acid; Described maleimide is the single maleimide containing unsaturated double-strand, comprises the one in N-hydroxyphenyl-maleimides HPM, N-phenylmaleimide N-PMI or N-carboxyl phenyl maleimide.
7. nano-TiO according to claim 2
2the preparation method of/maleimide phenolic aldehyde In-situ reaction resin, is characterized in that: described coupling agent is one or more in N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane KH792, γ-aminopropyl triethoxysilane KH550, γ-glycidyl ether oxygen propyl trimethoxy silicane KH560 or γ-(methacryloxypropyl) propyl trimethoxy silicane KH570; Described dispersion agent is the one in polyphosphoric acid type, polysilicon acid class, polycarboxylic acid, polyester type or polyether-type hyper-dispersant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310465092.6A CN103524691B (en) | 2013-10-08 | 2013-10-08 | Nano-TiO 2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310465092.6A CN103524691B (en) | 2013-10-08 | 2013-10-08 | Nano-TiO 2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103524691A CN103524691A (en) | 2014-01-22 |
| CN103524691B true CN103524691B (en) | 2016-01-06 |
Family
ID=49927076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310465092.6A Expired - Fee Related CN103524691B (en) | 2013-10-08 | 2013-10-08 | Nano-TiO 2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103524691B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107457712A (en) * | 2017-08-09 | 2017-12-12 | 安徽昌悌进出口贸易有限公司 | A kind of resin base high abrasion emery wheel material and preparation method thereof |
| CN111604043A (en) * | 2020-04-28 | 2020-09-01 | 山东科技大学 | Inorganic nonmetallic mineral composite material loaded with titanium dioxide layer and preparation method |
| CN114478850B (en) * | 2020-10-27 | 2023-08-15 | 广东生益科技股份有限公司 | Maleimide modified active ester and preparation method and application thereof |
| CN114649123B (en) * | 2022-04-11 | 2022-10-14 | 贝迪斯电子有限公司 | Manufacturing method of high-temperature-resistant flame-retardant precise metal film resistor |
-
2013
- 2013-10-08 CN CN201310465092.6A patent/CN103524691B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 周大鹏等.N-苯基马来酰亚胺改性酚醛树脂的合成及其结构性能.《化工学报》.2005,第56卷(第10期),第1987-1992页. * |
| 车剑飞等.纳米TiO2改性硼酚醛及其在摩擦材料中的应用.《非金属矿》.2001,第24卷(第3期),第49-51页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103524691A (en) | 2014-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103524691B (en) | Nano-TiO 2/ maleimide phenolic aldehyde In-situ reaction resin and preparation method thereof | |
| CN104861650A (en) | Heat-resistant benzoxazine resin and preparation method thereof | |
| CN105255112B (en) | A kind of epoxy resin fulvene compounding material and preparation method thereof | |
| CN102642830A (en) | Method for preparing graphene modified by silane coupling agent | |
| CN100523087C (en) | Thermostable benzoxazine resin compound and its preparation method and uses | |
| CN104231624A (en) | Modified cyanate resin heat-conducting composite material and preparation method thereof | |
| CN109762111B (en) | Bismaleimide ink for 3D printing and preparation method and application thereof | |
| CN109880283A (en) | A kind of preparation method of the nano-silicon dioxide modified phenolic resin of surface modification | |
| CN104761243A (en) | Method for preparing ceramic core by combining thermosetting organic silicon resin with ceramic powder | |
| CN103396653A (en) | Preparation method of graphene nanoplatelet/epoxy resin nanocomposite material | |
| CN103146141A (en) | Low dielectric constant polyhedral oligomeric silsesquioxane (POSS)/ epoxy resin hybrid material and preparation method | |
| CN103012790B (en) | Bisphthalonitrile-amino phenoxy phthalonitrile copolymer and condensate, and glass fiber composite material and preparation method thereof | |
| CN105482453A (en) | Low thermal expansion coefficient cyanate ester resin composite and preparation method thereof | |
| CN103709348A (en) | Production method for anti-ablation temperature-resistant phenolic resin | |
| CN101891936B (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN101885901A (en) | Biphenyl-structure-contained epoxy resin/montmorillonite nano composite material | |
| CN101864076A (en) | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof | |
| CN103408893B (en) | Maleimide phenolic resin/nano-TiO2 composite material and preparation method thereof | |
| CN104086729B (en) | A kind of dimethylbenzene phenol-formaldehyde resin modified and the method preparing water discharging board thereof | |
| CN110628170B (en) | Graphene oxide-phenolic aerogel material based on silane modification and preparation method thereof | |
| CN109096753B (en) | Nitrile resin composite material and preparation method thereof | |
| CN102643517A (en) | Method for preparing composite material by blending PHQEP/montmorillonite and modified epoxy resin | |
| CN103421277B (en) | Based on the preparation method of the epoxy resin composite material of nano oxidized silicon grain | |
| CN105694033B (en) | A kind of o-phthalonitrile resin composition and preparation method thereof and application method | |
| CN113861362A (en) | Method for rapidly curing and simultaneously toughening benzoxazine resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160106 Termination date: 20211008 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |