CN106117964A - A kind of modified boron containing phenolic resin and preparation method and application - Google Patents
A kind of modified boron containing phenolic resin and preparation method and application Download PDFInfo
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- CN106117964A CN106117964A CN201610473402.2A CN201610473402A CN106117964A CN 106117964 A CN106117964 A CN 106117964A CN 201610473402 A CN201610473402 A CN 201610473402A CN 106117964 A CN106117964 A CN 106117964A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a kind of modified boron containing phenolic resin and preparation method and application, its raw materials by weight portion includes boron bakelite resin 65 70 parts, esters of silicon acis 50 200 parts or titanate esters 0.5 2 parts.During preparation, esters of silicon acis or titanate esters are dropped in boron bakelite resin, under mix homogeneously room temperature, react 2～5h,.The modified boron containing phenolic resin solution of the present invention places 3 months still clear homogeneous in room temperature, the solid matters such as boric acid are not had to separate out, quality retention rate also significantly improves, and this modified boron containing phenolic resin is used for can improving in flame-proof composite material, functional paint, the firming agent of epoxy resin, rubber modifier etc. heat stability and the anti-flammability of product.Preparation method of the present invention is simple, does not use catalyst, there is not the indivisible hidden danger brought of catalyst.
Description
Technical field
The present invention relates to the technical field of phenol-formaldehyde resin modified and its preparation method and application, particularly relate to a kind of with miscellaneous
A kind of modified boron containing phenolic resin that atom modified boron bakelite resin obtains and preparation method and application.
Background technology
Phenolic resin starting material is easy to get, cheap, excellent heat resistance, shows greatly in resistance to thermal-protect ablation material field
Application potential.Compared with other organic resins, phenolic resin is that quality is protected as the advantage that ablation resistant material matrix resin is main
Stay rate high, but phenolic resin is degraded seriously during high temperature ablation, the excessively ablation such as rhegmalypt, groove occurs through often after ablation
With unstable ablation phenomen.For this technical staff, phenolic resin is carried out substantial amounts of study on the modification, generally at modified phenolic resin
Introducing resistant to elevated temperatures hetero atom (Si, B, N) etc. in the organism of fat, the material system (i.e. phenol-formaldehyde resin modified) of formation is in solidification
With in ablation process, react with the reactive group in phenolic resin with the hetero atom of active reactive group, formed and there is high solution
The keys such as C-B, C-Si, the N-Si from energy.Due to the existence of high dissociation energy chemical bond, the decomposition temperature energy that phenol-formaldehyde resin modified is initial
Enough raisings, thus improve the heat resistance of material system；Meanwhile, phenol-formaldehyde resin modified is during high temperature ablation, and quality retains
Rate is improved, and reduces ablation degree.
At present, the most useful organosilicon removes modified boron containing phenolic resin, and its preparation is general uses saligenin method, is i.e. preparing boron phenol
Dehydration later stage during urea formaldehyde add organosilicon modifier (as terminal hydroxy group organosilicon preformed polymer, Silane coupling agent KH550,
Phenyl triethoxysilane, tetramethoxy-silicane etc.), obtain organic-silicon-modified boron bakelite resin.But organic-silicon-modified boron phenol
Urea formaldehyde or there is dispersion problem, or quality retention rate is relatively low, it is impossible to extensively apply.
At present, in titanium modified boron containing phenolic resin, one nano-TiO2Particle modified boron bakelite resin, but nano-TiO2
Particle easily reunites in reaction system, it is uneven to disperse.Another kind of titanate esters modified boron containing phenolic resin of using, but titanate esters is met
Water reacts rapidly generation TiO2Precipitation, and addition is few, reacts wayward, easily gel, is hardly formed homogeneous solution, and
Preservation must be sealed, in case causing metatitanic acid ester linkage hydrolyzing after Xi Shui and generating precipitation.Additionally, under nitrogen atmosphere when 800 DEG C,
Though the quality retention rate of titanium modified boron containing phenolic resin can reach 73.3%, but need to use toluene to make solvent, expensive, have one
Fixed toxicity, and toluene boiling point is high, is difficult to remove in follow-up forming process.
Visible, existing titanium modified boron containing phenolic resin there is also the quality retention rate of 800 DEG C and dispersibility can not be expired simultaneously
The problem of foot.
Additionally, the patent application of Publication No. 102329474A uses zinc acetate, ammonia prepare boron phenol as catalyst
Urea formaldehyde, then with esters of silicon acis, titanate esters, graphite, molybdenum bisuphide, aluminium sesquioxide, zirconium oxide, carborundum etc. in organic solvent
Mix homogeneously forms solution, then adds glass fibre or carbon fiber, prepares the double modified boron containing phenolic resin composite material of silicon titanium.
The quality retention rate of this material 800 DEG C is about 75%, however the method employs ammonia, zinc acetate makees catalyst, in the later stage
Forming process has ammonia effusion, damages the healthy of operator；Alkali metal ion Zn2+Also the electrical property of material can be produced
Adverse effect；And along with the carrying out of reaction, the viscosity of reaction system is increasing, boric acid is difficult to react completely, still suffers from point
Dissipate sex chromosome mosaicism.
Above-mentioned phenol-formaldehyde resin modified, in addition to disadvantages described above, is required for using catalyst, the catalysis of introducing in preparation process
Agent is difficult to eliminate at last handling process, and the alkaline-earth metal in catalyst easily makes bullet guide generation communicating interrupt, causes
Bullet precision strike hydraulic performance decline；Or make rocket engine generation wake flow, reduce the antioxygenic property of material.Change it addition, above
Property phenolic resin in building-up process in order to reduce the existence of free phenol, can add excess boric acid, unreacted boric acid can precipitate
Get off, cause resin and the layering of unreacted boric acid, cause the phenol-formaldehyde resin modified dispersibility finally given to go wrong；And close
Cheng Zhonghui produces substantial amounts of waste water, pollutes environment.
Summary of the invention
It is an object of the invention to for technological deficiency present in prior art, first aspect, it is provided that a kind of high-quality is protected
Staying the modified boron containing phenolic resin of rate and good dispersion, by weight, its raw material includes following component:
Boron bakelite resin: 65-70 part (Mn=400-1000, Mw=700-2400)；
Esters of silicon acis: 50-200 part (preferably 100-180 part, more preferably 100-120 part)；Or
Titanate esters: 0.5-2 part (preferably 1-2 part, more preferably 1-1.3).
The esters of silicon acis combination of one or more in tetraethyl orthosilicate, positive isopropyl silicate and methyl silicate, mixed
Composition and division in a proportion example does not limit.
The titanate esters combination of one or more in tetraethyl titanate, isopropyl titanate and butyl titanate, mixed proportion
Do not limit.
Esters of silicon acis or titanate esters are dropped in boron bakelite resin, reacts 2～5h under mix homogeneously room temperature, i.e. obtain silicon and change
Property boron bakelite resin or titanium modified boron containing phenolic resin；Described boron bakelite resin is boron bakelite resin blocks of solid, boron bakelite resin
Powder or boron bakelite resin solution.
The preparation of described boron bakelite resin comprises the following steps:
1. after being heated to phenol melting, in sucting reaction still；
Boric acid is added the most under agitation in melted phenol, after being to slowly warm up to 140 DEG C of reactions 1-3 hour, by
Gradually it is warming up to 164 DEG C react 2-4 hour；
It is gradually heating to 181 DEG C the most again, fraction occurs, when the fraction weight of less than 98 DEG C reach the 0.1-of phenol quality
Stop heating when 0.2 times, discard fraction, reactor is boric acid phenol ester；
The most then boric acid phenol ester is cooled to less than 60 DEG C, adds paraformaldehyde in batches, be to slowly warm up to reactant
It it is boiling reflux；
5. decompression dehydration is started, when the gel time of reaction system reaches 140s (when 200 ± 1 DEG C) after backflow 20-60min
Within (preferably 45-70s), reaction terminates, and obtains described boron bakelite resin；Solvent can also be added at described boron bakelite resin
(weight of solvent is the 30～60% of phenol addition quality, preferably 56%), obtains boron bakelite resin solution after dissolving cooling.
Ratio, phenol: boric acid: the mol ratio of paraformaldehyde is 1:(0.1-0.5): (1.1-1.2).
Solvent in described boron bakelite resin solution is dehydrated alcohol, industrial alcohol, acetone, oxolane or ethylene glycol bisthioglycolate
Methyl ether.
Second aspect, it is provided that one does not use catalyst, the method preparing above-mentioned modified boron containing phenolic resin, weigh boron phenolic aldehyde
Toner 65-70 part and esters of silicon acis 50-200 part, or weigh boron-containing phenolic resin powder 65-70 part and titanate esters 0.5-2 part, will
Esters of silicon acis or titanate esters drop in boron-containing phenolic resin powder, react 2～5h, i.e. obtain Si modification boron phenol under mix homogeneously room temperature
Urea formaldehyde or titanium modified boron containing phenolic resin；Boron bakelite resin blocks of solid 65-70 part and esters of silicon acis 50-200 part can also be weighed,
Or weigh boron bakelite resin blocks of solid 65-70 part and titanate esters 0.5-2 part, esters of silicon acis or titanate esters are dropped to the boron melted
In phenolic resin blocks of solid, react 2～5h under mix homogeneously room temperature, i.e. obtain Si modification boron bakelite resin or titanium modification boron phenol
Urea formaldehyde；Boron bakelite resin solution 100 parts and esters of silicon acis 50-200 part of 65-70wt% can also be weighed, or weigh 65-
The boron bakelite resin solution of 70wt% 100 parts and titanate esters 0.5-2 part, drop to boron bakelite resin by esters of silicon acis or titanate esters molten
In liquid, react 2～5h under mix homogeneously room temperature, i.e. obtain Si modification boron bakelite resin solution or titanium modified boron containing phenolic resin is molten
Liquid.
The preparation of described boron bakelite resin comprises the following steps:
1. after being heated to phenol melting, in sucting reaction still；
Boric acid is added the most under agitation in melted phenol, after being to slowly warm up to 140 DEG C of reactions 1-3 hour, by
Gradually it is warming up to 164 DEG C react 2-4 hour；
It is gradually heating to 181 DEG C the most again, fraction occurs, when the fraction weight of less than 98 DEG C reach the 0.1-of phenol quality
Stopping heating when 0.2 times, the material in reactor is boric acid phenol ester；
The most then boric acid phenol ester is cooled to less than 60 DEG C, adds paraformaldehyde in batches, be to slowly warm up to reactant
It it is boiling reflux；
5. decompression dehydration is started, when the gel time of reaction system reaches 140s (when 200 ± 1 DEG C) after backflow 20-60min
Within (preferably 45-70s), reaction terminates, and obtains described boron bakelite resin；Solvent can also be added in described boron bakelite resin
(weight of solvent is the 30～60% of phenol addition quality, preferably 56%), obtains described boron bakelite resin after dissolving cooling molten
Liquid；
Preferably, ratio, phenol: boric acid: the mol ratio of paraformaldehyde is 1:(0.1-0.5): (1.1-1.2)；
It is furthermore preferred that the solvent in boron bakelite resin solution is dehydrated alcohol, industrial alcohol, acetone, oxolane or glycol dinitrate
Ether.
The third aspect, it is provided that above-mentioned modified boron containing phenolic resin is preparing flame-proof composite material, functional paint, epoxy resin
Application in firming agent, rubber modifier.
Compared with prior art, the invention has the beneficial effects as follows:
The modified boron containing phenolic resin that the present invention provides solves the problem of hetero atom phenol-formaldehyde resin modified bad dispersibility, this
The solution of the bright modified boron containing phenolic resin obtained is highly uniform, places 3 months still clear homogeneous in room temperature, does not has the solids such as boric acid
Material separates out.Modified boron containing phenolic resin after solidification can form the higher B-O key of bond energy, Si-O key and Ti-O key, at least keeps
Or (boron bakelite resin is 69.9%, and Si modification boron bakelite resin is 74.3%, titanium modification boron to be effectively improved quality retention rate
Phenolic resin is 68%), at least keep or improve anti-yaw damper performance and mechanical property.It is used for hindering by this modified boron containing phenolic resin
Retardant composite material, functional paint, the firming agent of epoxy resin, rubber modifier etc. can improve heat stability and the resistance of product
Combustion property.
The modified boron containing phenolic resin of the present invention, only needs at room temperature to drip esters of silicon acis in boron bakelite resin or titanate esters is stirred
Mix.Course of reaction will not concentrate heat release, does not produce implode phenomenon, and the solidification temperature of modified boron containing phenolic resin is low, 200 DEG C
Just can solidify below, existing curing apparatus all can realize.Owing to modified boron containing phenolic resin solution viscosity of the present invention compares
Low, make prepreg at normal temperatures or the conventional process such as premix material is wound, molds, lamination just can molding, to molding
The strong adaptability of technique.
Additionally, the preparation method of modified boron containing phenolic resin of the present invention can use ethanol or ethanol make solvent, the most pungent
Abnormal smells from the patient, and avirulence, preparation method is simple, does not use catalyst, there is not the catalyst indivisible hidden danger brought during preparation.
Accompanying drawing explanation
Fig. 1 show the infrared spectrogram of embodiment 1 Si modification boron bakelite resin；
Fig. 2 show boron bakelite resin TGA figure in a nitrogen atmosphere to scheme with DTG；
Fig. 3 show embodiment 1 Si modification boron bakelite resin TGA figure in a nitrogen atmosphere to scheme with DTG；
Fig. 4 show ethanol solution and the embodiment 5-6 titanium modification boron phenolic aldehyde tree of embodiment 1-2 Si modification boron bakelite resin
The photo of the THF solution of fat；
Fig. 5 show the photo of embodiment 5 titanium modified boron containing phenolic resin solidfied material；
Fig. 6 show boron bakelite resin TGA figure under oxygen atmosphere and DTG schemes；
Fig. 7 show embodiment 1 Si modification boron bakelite resin TGA figure under oxygen atmosphere and DTG schemes；
Fig. 8 show the infrared spectrogram of embodiment 5 titanium modified boron containing phenolic resin；
Fig. 9 show TGA figure and the DTG figure of embodiment 5 titanium modified boron containing phenolic resin；
Figure 10 show ethanol solution and the comparative example 4 titanium modification boron phenolic aldehyde tree of comparative example 1-2 Si modification boron bakelite resin
The photo of the THF solution of fat.
Detailed description of the invention
The modified boron containing phenolic resin of the present invention by introducing silicon or titanium in boron bakelite resin, make esters of silicon acis and titanate esters with
Boron bakelite resin reacts, and produces inorganic Si-O-Si or Ti-O-Ti network, part in the macromolecular chain of boron bakelite resin
The hydrogen of phenolic hydroxyl group is replaced by hetero atom silicon or titanium, thus the fragility overcoming phenolic hydroxyl group water suction and causing is big, easy to crack, mechanical by force
The lower degradation defect of degree.It addition, flexibility is bigger after introducing-Si-O-or-Ti-O-key in boron bakelite resin molecule so that be made from
Product fragility make moderate progress, toughness is greatly improved (as it is shown in figure 5, the angle of bend of the titanium modified boron containing phenolic resin of the present invention
Can reach about 45 °)；Owing to after solidification, silicon or titanium are four-way cross-linked structure, make the ablation resistance of product at least with general boron phenol
Urea formaldehyde is the best.
The modified boron containing phenolic resin of the present invention, its raw materials by weight portion includes following component:
Boron bakelite resin 65-70 part or boron bakelite resin solution 100 parts of (Mn=400-1000 of boron bakelite resin, Mw=
700-2400, weight/mass percentage composition in the solution is 65wt%-70wt%)；
Esters of silicon acis: 50-200 part (preferably 100-180 part, more preferably 100-120 part)；Or
Titanate esters: 0.5-2 part (preferably 1-2 part, more preferably 1-1.3 part).
Wherein, one or more during esters of silicon acis can be tetraethyl orthosilicate, positive isopropyl silicate and methyl silicate
Combination, mixed proportion does not limit；Titanate esters can be one or more in tetraethyl titanate, isopropyl titanate and butyl titanate
Combination, mixed proportion does not limit；Boron bakelite resin is commercially available, it is also possible to prepare as follows:
2. by melted phenol vacuum pump sucting reaction still；
Add boric acid the most while stirring, be to slowly warm up to 140 DEG C (heating rate is about 3-8 DEG C/10min) reaction 1-3 little
Shi Hou, is gradually heating to 164 DEG C (heating rate is about 1-2 DEG C/10min) reaction 2-4 hour；
It is gradually heating to the most again 181 DEG C (heating rate is about 1-2 DEG C/10min), controls the column head temperature on reactor not
More than 98 DEG C, collect fraction, stop heating, i.e. fraction weight when fraction weight reaches 0.1-0.2 times of phenol addition quality
When adding the 10-20% of quality for phenol, stopping heating, discard fraction, the product in reactor is i.e. boric acid phenol ester；
The most then boric acid phenol ester is cooled to less than 60 DEG C, adds paraformaldehyde in batches, be to slowly warm up to 110 DEG C with
It is upper that (heating rate is about 1-8 DEG C/10min, heats up too fast, causes concentrating heat release, can produce implode phenomenon；Heated up slow, reaction
Not exclusively.), come to life to reaction system and backflow occurs；
5. decompression dehydration is started, when the gel time of reaction system reaches 140s (when 200 ± 1 DEG C) after backflow 20-60min
Within (preferably 45-70s), reaction terminates, and obtains boron bakelite resin；In order to easily pour out from reactor, facilitate prepreg etc.
Later stage uses, and (weight of solvent is that phenol adds the 30～60% of quality, preferably can to add solvent in boron bakelite resin
56%) boron bakelite resin solution is obtained after, dissolving cooling.
Ratio, phenol: boric acid: the mol ratio of paraformaldehyde is 1:(0.1-0.5): (1.1-1.2).
Solvent in boron bakelite resin solution is dehydrated alcohol, industrial alcohol, acetone, oxolane or glycol dinitrate
Ether.
The method preparing modified boron containing phenolic resin of the present invention is: 1) use boron bakelite resin blocks of solid: weigh by weight
Boron bakelite resin blocks of solid 65-70 part, esters of silicon acis 50-200 part or titanate esters 0.5-2 part, drip esters of silicon acis or titanate esters
To melted boron bakelite resin blocks of solid, under mix homogeneously room temperature, react 2～5h, i.e. obtain Si modification boron bakelite resin or
Titanium modified boron containing phenolic resin；
2) boron-containing phenolic resin powder is used: pulverized by boron bakelite resin blocks of solid, weigh boron bakelite resin powder by weight
End 65-70 part, esters of silicon acis 50-200 part or titanate esters 0.5-2 part, drop to boron-containing phenolic resin powder by esters of silicon acis or titanate esters
In, react 2～5h under mix homogeneously room temperature, i.e. obtain Si modification boron bakelite resin or titanium modified boron containing phenolic resin；
3) boron bakelite resin solution is used: weigh the boron bakelite resin solution containing 65-70wt% boron bakelite resin by weight
100 parts, esters of silicon acis 50-200 part or titanate esters 0.5-2 part, drop to esters of silicon acis or titanate esters in boron bakelite resin solution, mixed
Close and under uniform room temperature, react 2～5h, i.e. obtain Si modification boron bakelite resin solution or titanium modified boron containing phenolic resin solution.
Below in conjunction with specific embodiment, further illustrate present disclosure, and the present invention is further elaborated, but
These embodiments limit the invention absolutely not.
The preparation of embodiment 1 Si modification boron bakelite resin
Prepare boron bakelite resin: in first melted phenol 956g being used vacuum mode sucting reaction still, add while stirring
Enter boric acid 155g, be to slowly warm up to 140 DEG C with the speed of 0.5 DEG C/min, be gradually heating to the speed of 0.2 DEG C/min subsequently
164 DEG C, then it is gradually heating to 181 DEG C with the speed of 0.1 DEG C/min, control column head temperature and be less than 98 DEG C, collect fraction, when evaporating
Point weight reaches to stop heating during 0.2 times of phenol weight, discards fraction.It is cooled to 60 DEG C；Add in reactor at twice
Paraformaldehyde 344g altogether, controlling programming rate is 0.2 DEG C/min, is to slowly warm up to more than 110 DEG C, comes to life to reaction system
Backflow occurs；Decompression dehydration is started after backflow 30-40min.When the gel time of reaction system, to reach 60s (200 ± 1 DEG C) the most anti-
Should terminate, add ethanol 536g, after dissolving cooling, obtain the ethanol solution of boron bakelite resin.
Prepare Si modification boron bakelite resin: the ethanol solution 1000g taking boron bakelite resin adds in reactor, by positive silicic acid
Ethyl ester 1070g adds in separatory funnel, drips complete within half an hour, and at room temperature reaction i.e. obtains Si modification boron phenol for 2 hours
The ethanol solution of urea formaldehyde.
(curve a is boron phenolic aldehyde tree as shown in Figure 1 for the boron bakelite resin of gained and the infrared spectrum of Si modification boron bakelite resin
The infrared spectrum of fat, curve b is the infrared spectrum of Si modification boron bakelite resin), Fig. 1 shows that boron, silicon all access phenolic resin chain
In rather than presented in simple physical blending in phenolic resin system.The 1350cm of curve a in figure-1Feature
Absworption peak belongs to B-O (boroxine) key, shows that boron element has successfully been grafted in phenolic resin.The 1074cm of curve b-1、
1158cm-1Place (1040-1200cm-1The peak at place broadly falls into the characteristic peak of Si-O key) it is the characteristic peak of Si-O key, silicon atom is described
Also it is grafted in boron bakelite resin with the form of chemical bond.
By ethanol solution and the ethanol solution sequencing liter respectively of Si modification boron bakelite resin of the boron bakelite resin of gained
Si modification boron bakelite resin solution or titanium modified boron containing phenolic resin solution (during solidification, are first reacted 2h at 120 DEG C, so by temperature solidification
After be warming up to 160 DEG C continue reaction 2h, be finally warming up to 180 DEG C reaction 2h.) pulverize afterwards, carry out thermal weight loss test, boron phenol
Thermal weight loss (TGA) curve of urea formaldehyde and Si modification boron bakelite resin and difference quotient thermogravimetric (DTG) curve are respectively such as Fig. 2 and Fig. 3 institute
Show.When TGA test heats up, boron bakelite resin can occur further curing reaction and release little molecule, and in corresponding diagram 2, DTG is bent
The mildest peak of 120-470 DEG C on line.In Fig. 2, DTG curve shows thermal weight loss peak occur 580-620 DEG C of thermal weight loss speed
Value, i.e. 580-620 DEG C is the decomposition temperature that maximum heat is weightless, divides mainly due to boron bakelite resin severe thermal in this temperature range
Solve.TGA curve in Fig. 2 can be seen that boron bakelite resin is 69.9% at the quality retention rate of 800 DEG C.
From figure 3, it can be seen that Si modification boron bakelite resin is weightless obvious between 50-100 DEG C, Si modification boron phenol is described
The solvent ethanol of urea formaldehyde is removed the most completely, and the viscosity being likely to be due to precuring later stage Si modification boron bakelite resin is excessive, little
Molecules of ethanol is difficult to volatilize.In Fig. 3, DTG curve shows thermal weight loss peak value, i.e. 630-occur 630-670 DEG C of thermal weight loss speed
670 DEG C is the decomposition temperature that maximum heat is weightless.
Comparison diagram 2 and Fig. 3 it can be seen that the heat stability that the introducing of hetero atom silicon makes boron bakelite resin improves, 800 DEG C
Quality retention rate under nitrogen atmosphere improves to 74.3% from 69.9%；Maximum heat decomposition rate is reduced to from 1.14%/min
0.45%/min, and maximum heat decomposition temperature from 605 DEG C improve to 640 DEG C.This is because the introducing of silicon makes boron bakelite resin
Presenting the borosilicate heterocycle structure of four sides crosslinking net in molecule, structure is more stable, and thermostability is more preferable.
The preparation of embodiment 2 Si modification boron bakelite resin
Prepare boron bakelite resin: in first melted phenol 956g being used vacuum mode sucting reaction still, add while stirring
Enter boric acid 155g, be to slowly warm up to 140 DEG C with the speed of 0.7 DEG C/min, be gradually heating to the speed of 0.1 DEG C/min subsequently
164 DEG C, then it is gradually heating to 181 DEG C with the speed of 0.2 DEG C/min, control column head temperature and be less than 98 DEG C, collect fraction, when evaporating
Point weight reaches to stop heating during 0.2 times of phenol.Fraction is cooled to 60 DEG C, adds paraformaldehyde 344g at twice, control
Programming rate is 0.1 DEG C/min, is to slowly warm up to more than 110 DEG C, and coming to life to reaction system backflow occurs；Backflow 30-
Decompression dehydration is started after 40min.Then react terminate when the gel time of reaction system reaches 50s (200 ± 1 DEG C), add ethanol
536g, obtains the ethanol solution of boron bakelite resin after dissolving cooling.
Prepare Si modification boron bakelite resin: the ethanol solution 100g taking boron bakelite resin adds in reactor, slowly heats up
Make it the most melted to 50-60 DEG C, each to positive isopropyl silicate and methyl silicate 86g is added in separatory funnel, half an hour
Interior dropping is complete, and reaction i.e. obtains the ethanol solution of Si modification boron bakelite resin for 2.5 hours.
Infrared spectrum, thermal weight loss (TGA) curve are all similar, the most further with embodiment 1 result with difference quotient thermogravimetric (DTG) curve
One repeats.
The preparation of embodiment 3 Si modification boron bakelite resin
Preparing boron bakelite resin: with embodiment 2, when preparing boron bakelite resin, final reaction terminates discharging immediately, is not added with second
Alcohol, i.e. obtains boron bakelite resin blocks of solid.
Prepare Si modification boron bakelite resin: take boron bakelite resin solid 70g and add in reactor, be to slowly warm up to 50-60
DEG C make it the most melted, tetraethyl orthosilicate 10g, positive isopropyl silicate 30g and methyl silicate 10g added in separatory funnel,
Drip complete within half an hour, react and i.e. obtain Si modification boron bakelite resin in 4 hours.
Infrared spectrum, thermal weight loss (TGA) curve are all similar, the most further with embodiment 1 result with difference quotient thermogravimetric (DTG) curve
One repeats.
The preparation of embodiment 4 Si modification boron bakelite resin
Prepare boron bakelite resin: with embodiment 2.
Prepare Si modification boron bakelite resin: take boron bakelite resin solid 70g, pulverized in addition reactor, by positive silicon
Acetoacetic ester 150g and positive isopropyl silicate 50g adds in separatory funnel, drips complete, react and i.e. obtain for 3 hours within half an hour
Si modification boron bakelite resin.
Infrared spectrum, thermal weight loss (TGA) curve are all similar, the most further with embodiment 1 result with difference quotient thermogravimetric (DTG) curve
One repeats.
Comparative example 1
Prepare boron bakelite resin: with embodiment 2.
Prepare Si modification boron bakelite resin: the ethanol solution 100g taking boron bakelite resin adds in reactor, by positive silicic acid
Ethyl ester 20g adds in separatory funnel, drips complete, obtain the second of Si modification boron bakelite resin after reacting 2 hours within half an hour
Alcoholic solution, but there is gelatin phenomenon in the ethanol solution of this Si modification boron bakelite resin, has significantly layering, illustrates that dispersibility reaches not
To solution requirement, it is impossible to for performance test.
Comparative example 2
Prepare boron bakelite resin: with embodiment 2.
Prepare Si modification boron bakelite resin: the ethanol solution 100g taking boron bakelite resin adds in reactor, by positive silicic acid
Ethyl ester 250g adds in separatory funnel, drips complete, obtain the second of Si modification boron bakelite resin after reacting 2 hours within half an hour
Alcoholic solution, but there is precipitation in the ethanol solution of this Si modification boron bakelite resin, has significantly layering, is not homogeneous system, explanation
Dispersibility does not reaches solution requirement, it is impossible to for performance test.
The preparation of embodiment 5 titanium modified boron containing phenolic resin
Prepare boron bakelite resin: in first melted phenol 956g being used vacuum mode sucting reaction still, add while stirring
Enter boric acid 210g, be to slowly warm up to 140 DEG C with the speed of 0.4 DEG C/min, be gradually heating to the speed of 0.1 DEG C/min subsequently
164 DEG C, then it is gradually heating to 181 DEG C with the speed of 0.1 DEG C/min, control column head temperature and be less than 98 DEG C, collect fraction, when evaporating
Point weight reaches to stop heating during 0.2 times of phenol, discards fraction, and the resultant product in reactor is boric acid phenol ester.By boron
Acid phenol ester is cooled to less than 60 DEG C；Adding paraformaldehyde 303g at twice, controlling heating rate is 0.5 DEG C/min, slowly rises
Temperature, to more than 110 DEG C, comes to life to reaction system and backflow occurs；Decompression dehydration is started after backflow 30-40min.Work as reactant
The gel time of system reaches 55s (200 ± 1 DEG C) and then react and terminate, and adds ethanol 536g, dissolves and obtains boron bakelite resin after lowering the temperature
Ethanol solution.
Prepare titanium modified boron containing phenolic resin: the ethanol solution 30g taking boron bakelite resin adds in reactor, by butyl titanate
0.3g is slowly added dropwise in reactor, at room temperature reaction 2 hours, adds 30g oxolane and continues reaction as solvent, until
The solution that brownish red is transparent occurs, i.e. obtains the THF solution of titanium modified boron containing phenolic resin.
The infrared spectrum of the titanium modified boron containing phenolic resin of gained is as shown in Figure 8.Fig. 8 shows that titanium accesses boron bakelite resin chain
In rather than presented in simple physical blending in boron bakelite resin system.1043cm in figure-1(butyl titanate
Methyl stretching vibration peak at 2950cm-1Place, and Fig. 8 does not has obvious absorption peaks in this position, illustrate that titanium is with phenol epoxide even
Connect) characteristic absorption peak belong to Ti-O (titanyl ester) key, show that titanium elements has successfully been grafted to boron phenol with the form of chemical bond
In urea formaldehyde.
By the THF solution of the titanium modified boron containing phenolic resin of gained sequencing elevated cure respectively (during solidification, first by Si modification
Boron bakelite resin solution or titanium modified boron containing phenolic resin solution react 2h at 120 DEG C, then heat to 160 DEG C and continue reaction 2h,
Finally it is warming up to 180 DEG C of reaction 2h.) pulverize afterwards, carry out thermal weight loss test, the thermal weight loss of titanium modified boron containing phenolic resin
(TGA) curve and difference quotient thermogravimetric (DTG) curve are as shown in Figure 9.From the TGA curve of Fig. 9 it can be seen that the introducing of hetero atom titanium can
To keep the heat stability of original boron bakelite resin, the quality retention rate under 800 DEG C of nitrogen atmospheres is 68%；DTG curve shows
Thermal weight loss peak value occur 590-630 DEG C of thermal weight loss speed, i.e. 590-630 DEG C is the decomposition temperature that maximum heat is weightless.
Comparison diagram 2 and Fig. 9 is it can be seen that thermal decomposition speed and the boron bakelite resin of titanium modified boron containing phenolic resin are suitable,
Big heat decomposition temperature improves to 620 DEG C from 605 DEG C.Hand over this is because the introducing of titanium makes to present four sides in boron bakelite resin molecule
The boron titana ring structure of networking shape, structure is more stable, and thermostability is more preferable.Although the addition of titanium does not significantly improve boron phenolic aldehyde tree
The quality retention rate of fat, but from fig. 5, it can be seen that the good toughness of titanium modified boron containing phenolic resin, hence it is evident that it is better than boron bakelite resin
(angle of bend of titanium modified boron containing phenolic resin is about 45 °, and the angle of bend of boron bakelite resin is only 160-180 °).The most just
It is to say, on the premise of the thermal stability being added in guarantee boron bakelite resin of titanium does not reduces, significantly improves boron bakelite resin
Mechanical property.
The preparation of embodiment 6 titanium modified boron containing phenolic resin
Prepare boron bakelite resin: with embodiment 5.
Prepare titanium modified boron containing phenolic resin: take boron bakelite resin 50g and add in reactor, be to slowly warm up to 50-60 DEG C and make
It is the most melted, and dropping 30g oxolane makes it dissolve, and slow cooling to room temperature, by tetraethyl titanate 0.5g and isopropyl titanate
0.5g is slowly added dropwise in reactor, at room temperature reaction 2 hours, then drips the continuation reaction of 70g oxolane, until there is palm fibre
The solution of red, transparent, i.e. obtains the THF solution of titanium modified boron containing phenolic resin.
Infrared spectrum, thermal weight loss (TGA) curve, difference quotient thermogravimetric (DTG) curve and angle of bend all with embodiment 5 result class
Seemingly, repeat the most one by one.
The preparation of embodiment 7 titanium modified boron containing phenolic resin
Prepare boron bakelite resin: with embodiment 5.
Prepare titanium modified boron containing phenolic resin: take boron bakelite resin 50g and add in reactor, be to slowly warm up to 50-60 DEG C and make
It is the most melted, and dropping 30g oxolane makes it dissolve, and slow cooling to room temperature, by tetraethyl titanate 0.05g, isopropyl titanate
0.1g and butyl titanate 0.1g is slowly added dropwise in reactor, at room temperature reaction 3 hours, then drips 30g oxolane and 50g
Glycol dimethyl ether continues reaction, until there is the solution that brownish red is transparent, i.e. obtains THF and the second of titanium modified boron containing phenolic resin
Glycol dimethyl ether solution.
Infrared spectrum, thermal weight loss (TGA) curve, difference quotient thermogravimetric (DTG) curve and angle of bend all with embodiment 5 result class
Seemingly, repeat the most one by one.
The preparation of embodiment 8 titanium modified boron containing phenolic resin
Prepare boron bakelite resin: with embodiment 5.
Prepare titanium modified boron containing phenolic resin: take boron bakelite resin 50g and add in reactor, be to slowly warm up to 50-60 DEG C and make
It is the most melted, and dropping 30g oxolane makes it dissolve, and slow cooling to room temperature, by tetraethyl titanate 0.4g and butyl titanate
0.1g is slowly added dropwise in reactor, at room temperature reaction 3 hours, then drips the continuation reaction of 85g oxolane, until there is palm fibre
The solution of red, transparent, i.e. obtains the THF solution of titanium modified boron containing phenolic resin.
Infrared spectrum, thermal weight loss (TGA) curve, difference quotient thermogravimetric (DTG) curve and angle of bend all with embodiment 5 result class
Seemingly, repeat the most one by one.
Comparative example 3
Prepare boron bakelite resin: with embodiment 5.
Prepare titanium modified boron containing phenolic resin: take boron bakelite resin 50g and add in reactor, be to slowly warm up to 50-60 DEG C and make
It is the most melted, and dropping 30g oxolane makes it dissolve, slow cooling to room temperature, is slowly added dropwise by butyl titanate 0.1g into anti-
Answer in still, at room temperature reaction 2 hours, then drip the continuation reaction of 100g glycol dimethyl ether, until occurring that brownish red is transparent
Solution, i.e. obtains the ethylene glycol dimethyl ether solution of titanium modified boron containing phenolic resin.The heat stability of this titanium modified boron containing phenolic resin with
Embodiment 5-8 no significant difference, but Toughness Ratio embodiment 5-8 is far short of what is expected, and slight curvature will fracture, angle of bend and enforcement
There were significant differences for example 5-8.
Comparative example 4
Prepare boron bakelite resin: with embodiment 5.
Prepare titanium modified boron containing phenolic resin: take boron bakelite resin 50g and add in reactor, be to slowly warm up to 50-60 DEG C and make
It is the most melted, and dropping 30g oxolane makes it dissolve, slow cooling to room temperature, is slowly added dropwise by butyl titanate 2.5g into anti-
Answer in still, at room temperature reaction 2.5 hours, then drip the continuation reaction of 90g glycol dimethyl ether, but brownish red can not be obtained
Transparent solution, reaction system deposited phenomenon, it is obvious that there is significantly layering, is not homogeneous system, illustrates that dispersibility does not reaches
Solution requirement, it is impossible to for performance test.
One, dispersibility experiment:
The ethanol solution of the Si modification boron bakelite resin that embodiment 1 and embodiment 2 obtain, embodiment 5 and embodiment 6 are obtained
The THF solution of the titanium modified boron containing phenolic resin arrived is observed after room temperature is placed 3 months, finds that solution is the most visibly homogeneous, clarifies, thoroughly
Bright, favorable dispersibility, see Fig. 4, be from left to right followed successively by embodiment 1, embodiment 2, embodiment 5 and embodiment 6.
Observe Si modification boron bakelite resin and the titanium modified boron containing phenolic resin of comparative example 1 to comparative example 4, find modified boron phenol
Urea formaldehyde or gelatin phenomenon occurs, or precipitation occurs, reaction system all has layering, it is impossible to obtain uniform solution body
System, dispersibility is very poor, sees Figure 10, is from left to right followed successively by comparative example 1, comparative example 2 and comparative example 4.
Two, non-oxidizability experiment:
The antioxygenic property of resin typically uses thermal weight loss (TGA) curve in oxygen atmosphere to be illustrated, tested tree
Fat sample under oxygen atmosphere with oxygen generation thermal degradation reaction, the final mass retention rate of resin sample is the biggest, non-oxidizability
The best.As a example by the boron bakelite resin and Si modification boron bakelite resin of embodiment 1, as shown in Figure 6, boron phenolic aldehyde tree under oxygen atmosphere
Fat quality retention rate at 800 DEG C is 39.7%；Si modification boron bakelite resin quality retention rate at 800 DEG C is
37.9%, as shown in Figure 7.Illustrate that the addition of silicon atom does not the most change the antioxygenic property of boron bakelite resin, can be as anti-
Ablator uses.
The Si modification boron bakelite resin of other embodiments and titanium modified boron containing phenolic resin all with the antioxidation of boron bakelite resin
Performance is suitable, and no significant difference repeats the most one by one.
The above is only the preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications
Also should be regarded as present disclosure.
Claims (10)
1. a modified boron containing phenolic resin, it is characterised in that by weight, its raw material includes following component:
Boron bakelite resin: 65-70 part (Mn=400-1000, Mw=700-2400)；
Esters of silicon acis: 50-200 part (preferably 100-180 part, more preferably 100-120 part)；Or
Titanate esters: 0.5-2 part (preferably 1-2 part, more preferably 1-1.3).
Modified boron containing phenolic resin the most according to claim 1, it is characterised in that esters of silicon acis is selected from tetraethyl orthosilicate, positive silicic acid
The combination of one or more in isopropyl ester and methyl silicate, mixed proportion does not limit.
Modified boron containing phenolic resin the most according to claim 1, it is characterised in that titanate esters is selected from tetraethyl titanate, metatitanic acid isopropyl
The combination of one or more in ester and butyl titanate, mixed proportion does not limit.
4. according to the arbitrary described modified boron containing phenolic resin of claim 1-3, it is characterised in that esters of silicon acis or titanate esters are dropped to
In boron bakelite resin, react 2～5h under mix homogeneously room temperature, i.e. obtain Si modification boron bakelite resin or titanium modification boron phenolic aldehyde tree
Fat；Described boron bakelite resin is boron bakelite resin blocks of solid, boron-containing phenolic resin powder or boron bakelite resin solution.
5. according to the arbitrary described modified boron containing phenolic resin of claim 1-4, it is characterised in that the preparation bag of described boron bakelite resin
Include following steps:
1. after being heated to phenol melting, in sucting reaction still；
In melted phenol, add boric acid the most under agitation, after being to slowly warm up to 140 DEG C of reactions 1-3 hour, gradually rise
Temperature is reacted 2-4 hour to 164 DEG C；
It is gradually heating to 181 DEG C the most again, fraction occurs, when the fraction weight of less than 98 DEG C reach 0.1-0.2 times of phenol quality
Time stop heating, discard fraction, reactor be boric acid phenol ester；
The most then boric acid phenol ester is cooled to less than 60 DEG C, adds paraformaldehyde in batches, be to slowly warm up to reaction system boiling
Rise backflow；
5. decompression dehydration is started, within the gel time of reaction system reaches 140s (when 200 ± 1 DEG C) after backflow 20-60min
(preferably 45-70s), reaction terminates, and obtains described boron bakelite resin；Solvent (solvent can also be added at described boron bakelite resin
Weight be phenol add quality 30～60%, preferably 56%), dissolve cooling after obtain boron bakelite resin solution.
Modified boron containing phenolic resin the most according to claim 5, it is characterised in that ratio, phenol: boric acid: poly first
The mol ratio of aldehyde is 1:(0.1-0.5): (1.1-1.2).
7. according to modified boron containing phenolic resin described in claim 5 or 6, it is characterised in that molten in described boron bakelite resin solution
Agent is dehydrated alcohol, industrial alcohol, acetone, oxolane or glycol dimethyl ether.
8. the method preparing the arbitrary described modified boron containing phenolic resin of claim 1-7, it is characterised in that weigh boron phenolic aldehyde tree
Cosmetics end 65-70 part and esters of silicon acis 50-200 part, or weigh boron-containing phenolic resin powder 65-70 part and titanate esters 0.5-2 part, by silicon
Acid esters or titanate esters drop in boron-containing phenolic resin powder, react 2～5h, i.e. obtain Si modification boron phenolic aldehyde under mix homogeneously room temperature
Resin or titanium modified boron containing phenolic resin；Boron bakelite resin blocks of solid 65-70 part and esters of silicon acis 50-200 part can also be weighed, or
Weigh boron bakelite resin blocks of solid 65-70 part and titanate esters 0.5-2 part, esters of silicon acis or titanate esters are dropped to the boron phenol melted
In urea formaldehyde blocks of solid, react 2～5h under mix homogeneously room temperature, i.e. obtain Si modification boron bakelite resin or titanium modification boron phenolic aldehyde
Resin；Boron bakelite resin solution 100 parts and esters of silicon acis 50-200 part of 65-70wt% can also be weighed, or weigh 65-70wt%
Boron bakelite resin solution 100 parts and titanate esters 0.5-2 part, esters of silicon acis or titanate esters are dropped in boron bakelite resin solution,
React 2～5h under mix homogeneously room temperature, i.e. obtain Si modification boron bakelite resin solution or titanium modified boron containing phenolic resin solution.
Method the most according to claim 8, it is characterised in that the preparation of described boron bakelite resin comprises the following steps:
1. after being heated to phenol melting, in sucting reaction still；
In melted phenol, add boric acid the most under agitation, after being to slowly warm up to 140 DEG C of reactions 1-3 hour, gradually rise
Temperature is reacted 2-4 hour to 164 DEG C；
It is gradually heating to 181 DEG C the most again, fraction occurs, when the fraction weight of less than 98 DEG C reach 0.1-0.2 times of phenol quality
Time stop heating, the material in reactor is boric acid phenol ester；
The most then boric acid phenol ester is cooled to less than 60 DEG C, adds paraformaldehyde in batches, be to slowly warm up to reaction system boiling
Rise backflow；
5. decompression dehydration is started, within the gel time of reaction system reaches 140s (when 200 ± 1 DEG C) after backflow 20-60min
(preferably 45-70s), reaction terminates, and obtains described boron bakelite resin；Solvent can also be added (molten in described boron bakelite resin
The weight of agent is the 30～60% of phenol addition quality, preferably 56%) and, after dissolving cooling, obtain described boron bakelite resin solution；
Preferably, ratio, phenol: boric acid: the mol ratio of paraformaldehyde is 1:(0.1-0.5): (1.1-1.2)；More excellent
Choosing, the solvent in boron bakelite resin solution is dehydrated alcohol, industrial alcohol, acetone, oxolane or glycol dimethyl ether.
10. modified boron containing phenolic resin described in claim is preparing the solidification of flame-proof composite material, functional paint, epoxy resin
Application in agent, rubber modifier.
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|---|---|---|---|---|
| CN110684315A (en) * | 2019-09-26 | 2020-01-14 | 江苏百利达股份有限公司 | Preparation process of high-uniformity phenolic resin |
| CN111410726A (en) * | 2020-05-19 | 2020-07-14 | 安徽凯沃科技有限公司 | High-carbon-residue phenolic resin and preparation method thereof |
| CN112194765A (en) * | 2020-12-04 | 2021-01-08 | 北京玻钢院复合材料有限公司 | Borosilicate phenolic resin suitable for hot-melt pre-dipping process, composite material and preparation method of borosilicate phenolic resin |
| CN116675820A (en) * | 2023-07-26 | 2023-09-01 | 天津大学 | Organosilicon modified boron phenolic resin and preparation method thereof |
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| CN111116213A (en) * | 2019-02-21 | 2020-05-08 | 张家港市恒乐阳方高温材料有限公司 | Dry refractory material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329474A (en) * | 2011-07-29 | 2012-01-25 | 太仓力达莱特精密工业有限公司 | Organosilicon and titanium modified boron containing phenolic resin composite material and preparation method thereof |
| CN102675572A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Application of organic silicon modifier in modified thermosetting phenolic resin |
| CN104817821A (en) * | 2015-04-10 | 2015-08-05 | 航天材料及工艺研究所 | SiO2-TiO2 inorganic hybrid thermosetting thermosetting phenolic resin and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089552A (en) * | 1989-12-08 | 1992-02-18 | The B. F. Goodrich Company | High char yield silazane-modified phenolic resins |
| CN102443181B (en) * | 2011-10-24 | 2013-04-10 | 太仓力达莱特精密工业有限公司 | Method for preparing thermosetting boron-containing phenolic resin powder |
| CN103435766B (en) * | 2013-08-30 | 2015-06-24 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
-
2016
- 2016-06-24 CN CN201811021332.2A patent/CN109265912B/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329474A (en) * | 2011-07-29 | 2012-01-25 | 太仓力达莱特精密工业有限公司 | Organosilicon and titanium modified boron containing phenolic resin composite material and preparation method thereof |
| CN102675572A (en) * | 2012-05-08 | 2012-09-19 | 浙江大学 | Application of organic silicon modifier in modified thermosetting phenolic resin |
| CN104817821A (en) * | 2015-04-10 | 2015-08-05 | 航天材料及工艺研究所 | SiO2-TiO2 inorganic hybrid thermosetting thermosetting phenolic resin and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684315A (en) * | 2019-09-26 | 2020-01-14 | 江苏百利达股份有限公司 | Preparation process of high-uniformity phenolic resin |
| CN111410726A (en) * | 2020-05-19 | 2020-07-14 | 安徽凯沃科技有限公司 | High-carbon-residue phenolic resin and preparation method thereof |
| CN112194765A (en) * | 2020-12-04 | 2021-01-08 | 北京玻钢院复合材料有限公司 | Borosilicate phenolic resin suitable for hot-melt pre-dipping process, composite material and preparation method of borosilicate phenolic resin |
| CN112194765B (en) * | 2020-12-04 | 2021-03-09 | 北京玻钢院复合材料有限公司 | Borosilicate phenolic resin suitable for hot-melt pre-dipping process, composite material and preparation method of borosilicate phenolic resin |
| CN116675820A (en) * | 2023-07-26 | 2023-09-01 | 天津大学 | Organosilicon modified boron phenolic resin and preparation method thereof |
| CN116675820B (en) * | 2023-07-26 | 2023-10-10 | 天津大学 | Organosilicon modified boron phenolic resin and preparation method thereof |
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