CN106117964B - A kind of modified boron containing phenolic resin and the preparation method and application thereof - Google Patents
A kind of modified boron containing phenolic resin and the preparation method and application thereof Download PDFInfo
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- CN106117964B CN106117964B CN201610473402.2A CN201610473402A CN106117964B CN 106117964 B CN106117964 B CN 106117964B CN 201610473402 A CN201610473402 A CN 201610473402A CN 106117964 B CN106117964 B CN 106117964B
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a kind of modified boron containing phenolic resin and the preparation method and application thereof, raw material includes 65-70 parts of boron bakelite resin in parts by weight, 50-200 parts of esters of silicon acis or 0.5-2 parts of titanate esters.Esters of silicon acis or titanate esters are added dropwise in boron bakelite resin when preparation, is uniformly mixed and reacts 2~5h at room temperature.Modified boron containing phenolic resin solution of the invention is in be placed at room temperature for 3 months still clear homogeneous, there is no the precipitation of the solid matters such as boric acid, quality retention rate also significantly improves, which is used in flame retardant composite material, functional paint, the curing agent of epoxy resin, rubber modifier etc. can be improved the thermal stability and anti-flammability of product.Preparation method of the present invention is simple, does not use catalyst, and the indivisible bring hidden danger of catalyst is not present.
Description
Technical field
The present invention relates to the technical fields of phenol-formaldehyde resin modified and its preparation method and application, more particularly to a kind of with miscellaneous
A kind of modified boron containing phenolic resin and the preparation method and application thereof that atom modified boron bakelite resin obtains.
Background technique
Phenolic resin starting material is easy to get, is 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 main advantage of ablation resistant material matrix resin
It is high to stay rate, but phenolic resin is degraded seriously during high temperature ablation, through often there is the excessive ablation such as rhegmalypt, groove after ablation
With unstable ablation phenomen.Technical staff has carried out a large amount of study on the modification to phenolic resin thus, usually in modified phenolic resin
Hetero atom resistant to high temperature (Si, B, N) etc. is introduced in the organism of rouge, the material system (i.e. phenol-formaldehyde resin modified) of formation is solidifying
In ablation process, the hetero atom with active reactive group is reacted with the reactive group in phenolic resin, and being formed has high solution
The keys such as C-B, C-Si, N-Si from energy.Due to the presence of high dissociation energy chemical bond, the initial decomposition temperature energy of phenol-formaldehyde resin modified
It is enough to improve, to improve the heat resistance of material system；Meanwhile phenol-formaldehyde resin modified, during high temperature ablation, quality retains
Rate is improved, and reduces ablation degree.
Currently, also useful organosilicon removes modified boron containing phenolic resin, preparation generally uses saligenin method, that is, is preparing boron phenol
Dehydration later period during urea formaldehyde be added organosilicon modifier (such as terminal hydroxy group organosilicon preformed polymer, Silane coupling agent KH550,
Phenyl triethoxysilane, tetramethoxy-silicane etc.), obtain organic-silicon-modified boron bakelite resin.However organic-silicon-modified boron phenol
Urea formaldehyde or there are dispersion problem or quality retention rate are lower, can not be widely applied.
Currently, in titanium modified boron containing phenolic resin, it is a kind of to use nano-TiO2Particle modified boron bakelite resin, however nano-TiO2
Particle is easy to reunite in the reaction system, disperse unevenly.Another kind titanate esters modified boron containing phenolic resin, but titanate esters are met
Water, which reacts rapidly, generates TiO2Precipitating, and additional amount is few, reaction is not easy to control, easily gel, it is hardly formed homogeneous solution, and
It must be sealed, generate precipitating to prevent causing metatitanic acid ester linkage hydrolyzing after water suction.In addition, under nitrogen atmosphere at 800 DEG C,
Though the quality retention rate of titanium modified boron containing phenolic resin can reach 73.3%, need to make using toluene solvent, it is expensive, have one
Fixed toxicity, and toluene boiling point is high, is difficult to remove in subsequent forming process.
As it can be seen that there is also 800 DEG C of quality retention rates and dispersibility to expire simultaneously for existing titanium modified boron containing phenolic resin
The problem of foot.
In addition, going out boron phenol as catalyst preparation using zinc acetate, ammonium hydroxide in the patent application of Publication No. 102329474A
Urea formaldehyde, then in organic solvent with esters of silicon acis, titanate esters, graphite, molybdenum disulfide, aluminum oxide, zirconium oxide, silicon carbide etc.
It is uniformly mixed and forms solution, glass fibre or carbon fiber is then added, prepare the double modified boron containing phenolic resin composite materials of silicon titanium.
The quality retention rate of 800 DEG C of the material is about 75%, however ammonium hydroxide, zinc acetate has been used to make catalyst in this method, in the later period
Ammonia evolution is had in forming process, damages the health of operator；Alkali metal ion Zn2+Also the electrical property of material can be generated
Adverse effect；And with the progress of reaction, the viscosity of reaction system is increasing, and boric acid is difficult to react completely, and there are still divide
Dissipate property problem.
Above-mentioned phenol-formaldehyde resin modified is required during the preparation process in addition to disadvantages described above using catalyst, the catalysis of introducing
Agent is difficult to eliminate in last handling process, and the alkaline-earth metal in catalyst is easy to make bullet guide that communicating interrupt occur, and causes
The decline of bullet precision strike performance；Or make rocket engine that wake flow occur, reduce the antioxygenic property of material.In addition, changing above
In the synthesis process in order to reduce the presence of free phenol, excessive boric acid can be added, unreacted boric acid can precipitate in property phenolic resin
Get off, causes resin and unreacted boric acid to be layered, finally obtained phenol-formaldehyde resin modified dispersibility is caused to go wrong；And it closes
Cheng Zhonghui generates a large amount of waste water, pollutes environment.
Summary of the invention
The purpose of the present invention is being directed to technological deficiency existing in the prior art, in a first aspect, providing a kind of high quality guarantor
The modified boron containing phenolic resin of rate and good dispersion is stayed, in parts by weight, raw material includes following component:
Boron bakelite resin: 65-70 parts (Mn=400-1000, Mw=700-2400)；
Esters of silicon acis: 50-200 parts (preferably 100-180 parts, 100-120 parts more preferable)；Or
Titanate esters: 0.5-2 parts (preferably 1-2 parts, more preferable 1-1.3).
Esters of silicon acis is selected from the combination of one or more of ethyl orthosilicate, positive isopropyl silicate and methyl orthosilicate, mixes
There is no limit for composition and division in a proportion example.
Titanate esters are selected from the combination of one or more of tetraethyl titanate, isopropyl titanate and butyl titanate, mixed proportion
There is no limit.
Esters of silicon acis or titanate esters are added dropwise in boron bakelite resin, 2~5h of reaction at room temperature is uniformly mixed and changes to get to silicon
Property boron bakelite resin or titanium modified boron containing phenolic resin；The boron bakelite resin is boron bakelite resin blocks of solid, boron bakelite resin
Powder or boron bakelite resin solution.
The preparation of the boron bakelite resin the following steps are included:
1. after phenol is heated to melting, in sucting reaction kettle；
2. boric acid is added into the phenol of melting under agitation, after being to slowly warm up to 140 DEG C of reactions 1-3 hours, by
Gradually it is warming up to 164 DEG C of reactions 2-4 hours；
3. being gradually heated to 181 DEG C again, there is fraction, when 98 DEG C of fraction weight below reach the 0.1- of phenol quality
Stop heating at 0.2 times, discard fraction, is boric acid phenol ester in reaction kettle；
4. boric acid phenol ester is then cooled to 60 DEG C hereinafter, paraformaldehyde is added in batches, it is to slowly warm up to reactant
It is boiling reflux；
5. starting decompression dehydration after reflux 20-60min, when the gel time of reaction system reaches 140s (at 200 ± 1 DEG C)
Within (preferably 45-70s), reaction terminates, and obtains the boron bakelite resin；Solvent can also be added in the boron bakelite resin
(weight of solvent is that phenol is added the 30~60% of quality, preferably 56%), obtains boron bakelite resin solution after dissolution cooling.
According to the molar ratio, phenol: boric acid: the molar ratio of paraformaldehyde is 1:(0.1-0.5): (1.1-1.2).
Solvent in the boron bakelite resin solution is dehydrated alcohol, industrial alcohol, acetone, tetrahydrofuran or ethylene glycol two
Methyl ether.
Second aspect provides one kind without using catalyst, and the method for preparing above-mentioned modified boron containing phenolic resin weighs boron phenolic
65-70 parts and esters of silicon acis 50-200 parts of toner, or 65-70 parts and titanate esters 0.5-2 parts of boron-containing phenolic resin powder are taken, it will
Esters of silicon acis or titanate esters are added dropwise in boron-containing phenolic resin powder, are uniformly mixed and are reacted 2~5h at room temperature to get Si modification boron phenol is arrived
Urea formaldehyde or titanium modified boron containing phenolic resin；65-70 parts and esters of silicon acis 50-200 parts of boron bakelite resin blocks of solid can also be weighed,
Or 65-70 parts and titanate esters 0.5-2 parts of boron bakelite resin blocks of solid are taken, esters of silicon acis or titanate esters are added dropwise to the boron of melting
In phenolic resin blocks of solid, it is uniformly mixed and reacts 2~5h at room temperature to get Si modification boron bakelite resin or the modified boron phenol of titanium is arrived
Urea formaldehyde；100 parts and esters of silicon acis 50-200 parts of boron bakelite resin solution of 65-70wt% can also be weighed, or take 65-
100 parts and titanate esters 0.5-2 parts of the boron bakelite resin solution of 70wt%, it is molten that esters of silicon acis or titanate esters are added dropwise to boron bakelite resin
In liquid, it is uniformly mixed and reacts 2~5h at room temperature to get molten to Si modification boron bakelite resin solution or titanium modified boron containing phenolic resin
Liquid.
The preparation of the boron bakelite resin the following steps are included:
1. after phenol is heated to melting, in sucting reaction kettle；
2. boric acid is added into the phenol of melting under agitation, after being to slowly warm up to 140 DEG C of reactions 1-3 hours, by
Gradually it is warming up to 164 DEG C of reactions 2-4 hours；
3. being gradually heated to 181 DEG C again, there is fraction, when 98 DEG C of fraction weight below reach the 0.1- of phenol quality
Stop heating at 0.2 times, the substance in reaction kettle is boric acid phenol ester；
4. boric acid phenol ester is then cooled to 60 DEG C hereinafter, paraformaldehyde is added in batches, it is to slowly warm up to reactant
It is boiling reflux；
5. starting decompression dehydration after reflux 20-60min, when the gel time of reaction system reaches 140s (at 200 ± 1 DEG C)
Within (preferably 45-70s), reaction terminates, and obtains the boron bakelite resin；Solvent can also be added in the boron bakelite resin
(weight of solvent is that phenol is added the 30~60% of quality, and it is molten preferably 56%), after dissolution cooling to obtain the boron bakelite resin
Liquid；
Preferably, according to the molar ratio, phenol: boric acid: the molar 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, tetrahydrofuran or glycol dinitrate
Ether.
The third aspect provides above-mentioned modified boron containing phenolic resin and is preparing flame retardant composite material, functional paint, epoxy resin
Application in curing agent, rubber modifier.
Compared with prior art, the beneficial effects of the present invention are:
Modified boron containing phenolic resin provided by the invention solves the problems, such as hetero atom phenol-formaldehyde resin modified bad dispersibility, this hair
The solution of bright obtained modified boron containing phenolic resin is highly uniform, in be placed at room temperature for 3 months still clear homogeneous, without solids such as boric acid
Substance is precipitated.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 keep
Or it effectively improves quality retention rate (boron bakelite resin 69.9%, Si modification boron bakelite resin is 74.3%, the modified boron of titanium
Phenolic resin is 68%), at least to keep or improve Burning corrosion resistance energy and mechanical property.The modified boron containing phenolic resin is used to hinder
Thermal stability and the resistance of product can be improved in retardant composite material, functional paint, the curing agent of epoxy resin, rubber modifier etc.
Combustion property.
Modified boron containing phenolic resin of the invention only needs that esters of silicon acis is added dropwise into boron bakelite resin at room temperature or titanate esters is stirred
It mixes.Reaction process will not concentrate heat release, not generate implode phenomenon, and the solidification temperature of modified boron containing phenolic resin is low, and 200 DEG C
It can be cured below, existing curing apparatus is able to achieve.Since modified boron containing phenolic resin solution viscosity of the present invention compares
It is low, it is made into prepreg at normal temperature or the conventional process such as premix is wound, is molded, being laminated can form, to molding
Technique it is adaptable.
In addition, ethyl alcohol can be used in the preparation method of modified boron containing phenolic resin of the present invention or alcohol makees solvent, it is not pungent
Smell, and non-toxic, preparation method is simple, and when preparation does not use catalyst, and the indivisible bring hidden danger of catalyst is not present.
Detailed description of the invention
Fig. 1 show the infrared spectrogram of 1 Si modification boron bakelite resin of embodiment；
Fig. 2 show the TGA figure and DTG figure of boron bakelite resin in a nitrogen atmosphere；
Fig. 3 show the TGA figure and DTG figure of 1 Si modification boron bakelite resin of embodiment in a nitrogen atmosphere；
Fig. 4 show ethanol solution and the modified boron phenolic tree of embodiment 5-6 titanium of embodiment 1-2 Si modification boron bakelite resin
The photo of the THF solution of rouge；
Fig. 5 show the photo of 5 titanium modified boron containing phenolic resin solidfied material of embodiment；
Fig. 6 show TGA figure and DTG figure of the boron bakelite resin under oxygen atmosphere；
Fig. 7 show TGA figure and DTG figure of the 1 Si modification boron bakelite resin of embodiment under oxygen atmosphere；
Fig. 8 show the infrared spectrogram of 5 titanium modified boron containing phenolic resin of embodiment；
Fig. 9 show the TGA figure and DTG figure of 5 titanium modified boron containing phenolic resin of embodiment；
Figure 10 show ethanol solution and the modified boron phenolic tree of 4 titanium of comparative example of comparative example 1-2 Si modification boron bakelite resin
The photo of the THF solution of rouge.
Specific embodiment
Modified boron containing phenolic resin of the invention by introducing silicon or titanium in boron bakelite resin, make esters of silicon acis and titanate esters with
Boron bakelite resin reacts, and inorganic Si-O-Si or Ti-O-Ti network, part are generated in the macromolecular chain of boron bakelite resin
The hydrogen of phenolic hydroxyl group is replaced by hetero atom silicon or titanium, so that it is big, easy to crack, mechanical strong to overcome brittleness caused by phenolic hydroxyl group water suction
The defects of degree decline.In addition, it is flexible larger after introducing-Si-O- or-Ti-O- key in boron bakelite resin molecule, so that being made from it
Product brittleness make moderate progress, toughness greatly improves (as shown in figure 5, the bending angle of titanium modified boron containing phenolic resin of the invention
It can reach about 45 °)；Since silicon or titanium are in four-way cross-linked structure after solidification, make the ablation resistance of product at least with general boron phenol
Urea formaldehyde is equally good.
Modified boron containing phenolic resin of the invention, raw material include following component in parts by weight:
65-70 parts of boron bakelite resin or boron bakelite resin solution 100 parts of (Mn=400-1000 of boron bakelite resin, Mw=
700-2400, mass percentage in the solution are 65wt%-70wt%)；
Esters of silicon acis: 50-200 parts (preferably 100-180 parts, 100-120 parts more preferable)；Or
Titanate esters: 0.5-2 parts (preferably 1-2 parts, 1-1.3 parts more preferable).
Wherein, esters of silicon acis can be one or more of ethyl orthosilicate, positive isopropyl silicate and methyl orthosilicate
Combination, there is no limit for mixed proportion；Titanate esters can be one or more of tetraethyl titanate, isopropyl titanate and butyl titanate
Combination, mixed proportion there is no limit；Boron bakelite resin is commercially available, and can also be prepared as follows:
2. by the phenol of melting in vacuum pump sucting reaction kettle；
2. boric acid is added while stirring, it is small to be to slowly warm up to 140 DEG C (heating rate is about 3-8 DEG C/10min) reaction 1-3
Shi Hou is gradually heated to 164 DEG C (heating rate is about 1-2 DEG C/10min) and reacts 2-4 hours；
3. being gradually heated to 181 DEG C (heating rate is about 1-2 DEG C/10min) again, the column head temperature on control reaction kettle is not
More than 98 DEG C, fraction is collected, stops heating, i.e. fraction weight when fraction weight reaches when 0.1-0.2 times of quality is added in phenol
When the 10-20% of quality is added for phenol, stops heating, discard fraction, the product in reaction kettle is boric acid phenol ester；
4. boric acid phenol ester is then cooled to 60 DEG C hereinafter, paraformaldehyde is added 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, is heated up too fast, causes to concentrate heat release, can generate implode phenomenon；It heated up slow, reacted
Not exclusively.), it flows back until reaction system comes to life；
5. starting decompression dehydration after reflux 20-60min, when the gel time of reaction system reaches 140s (at 200 ± 1 DEG C)
Within (preferably 45-70s), reaction terminates, and obtains boron bakelite resin；In order to be easy to pour out from reaction kettle, facilitate prepreg etc.
Later period uses, and solvent can be added into boron bakelite resin, and (weight of solvent is that phenol is added the 30~60% of quality, preferably
56%), boron bakelite resin solution is obtained after dissolution cooling.
According to the molar ratio, phenol: boric acid: the molar 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, tetrahydrofuran or glycol dinitrate
Ether.
The method for preparing modified boron containing phenolic resin of the present invention are as follows: 1) use boron bakelite resin blocks of solid: weighing by weight
Esters of silicon acis or titanate esters are added dropwise for 65-70 parts of boron bakelite resin blocks of solid, 50-200 parts of esters of silicon acis or 0.5-2 parts of titanate esters
Into the boron bakelite resin blocks of solid of melting, be uniformly mixed at room temperature 2~5h of reaction to get to Si modification boron bakelite resin or
Titanium modified boron containing phenolic resin；
2) it uses boron-containing phenolic resin powder: boron bakelite resin blocks of solid being crushed, weighs boron bakelite resin powder by weight
65-70 parts last, 50-200 parts of esters of silicon acis or 0.5-2 parts of titanate esters, are added dropwise to boron-containing phenolic resin powder for esters of silicon acis or titanate esters
In, it is uniformly mixed and reacts 2~5h at room temperature to get Si modification boron bakelite resin or titanium modified boron containing phenolic resin is arrived；
3) it uses boron bakelite resin solution: weighing the boron bakelite resin solution of the boron bakelite resin containing 65-70wt% by weight
100 parts, 50-200 parts of esters of silicon acis or 0.5-2 parts of titanate esters, esters of silicon acis or titanate esters are added dropwise in boron bakelite resin solution, are mixed
It closes and reacts 2~5h at room temperature uniformly to get Si modification boron bakelite resin solution or titanium modified boron containing phenolic resin solution is arrived.
Below in conjunction with specific embodiment, the content of the present invention will be explained in more detail, and the present invention is further elaborated, but
These embodiments limit the invention absolutely not.
The preparation of 1 Si modification boron bakelite resin of embodiment
Prepare boron bakelite resin: first by the phenol 956g of melting using in vacuum mode sucting reaction kettle, while stirring plus
Enter boric acid 155g, is to slowly warm up to 140 DEG C with the rate of 0.5 DEG C/min, is then gradually heated to the rate of 0.2 DEG C/min
164 DEG C, then be gradually heated to 181 DEG C with the rate of 0.1 DEG C/min, control column head temperature is no more than 98 DEG C, collects fraction, when evaporating
Point weight stops heating when reaching 0.2 times of phenol weight, discards fraction.It is cooled to 60 DEG C；It is added in two times into reaction kettle
The total 344g of paraformaldehyde, control heating rate are 0.2 DEG C/min, 110 DEG C or more are to slowly warm up to, until reaction system comes to life
It flows back；Start decompression dehydration after reflux 30-40min.When the gel time of reaction system reaches 60s (200 ± 1 DEG C) then instead
It should terminate, ethyl alcohol 536g is added, obtains the ethanol solution of boron bakelite resin after dissolution cooling.
It prepares Si modification boron bakelite resin: taking the ethanol solution 1000g of boron bakelite resin to be added in reaction kettle, by positive silicic acid
Ethyl ester 1070g is added in separatory funnel, in being added dropwise in half an hour, reacts 2 hours at room temperature and obtains Si modification boron phenol
The ethanol solution of urea formaldehyde.
(curve a is boron phenolic tree to the infrared spectroscopy of resulting boron bakelite resin and Si modification boron bakelite resin as shown in Figure 1
The infrared spectroscopy of rouge, curve b are the infrared spectroscopy of Si modification boron bakelite resin), Fig. 1 shows that boron, silicon access phenolic resin chain
In, rather than be present in phenolic resin system in the form of simple physical blending.The 1350cm of curve a in figure-1Feature
Absorption 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-1Locate (1040-1200cm-1The peak at place belongs to the characteristic peak of Si-O key) be Si-O key characteristic peak, illustrate silicon atom
Also it is grafted in boron bakelite resin in the form of chemical bond.
The ethanol solution of the ethanol solution of resulting boron bakelite resin and Si modification boron bakelite resin is distinguished into sequencing liter
Temperature solidification is (when solidification, first by Si modification boron bakelite resin solution or titanium modified boron containing phenolic resin solution in 120 DEG C of reaction 2h, so
After be warming up to 160 DEG C the reaction was continued 2h, be finally warming up to 180 DEG C of reaction 2h.) crush afterwards, carry out thermal weight loss test, boron phenol
Thermal weight loss (TGA) curve and difference quotient thermogravimetric (DTG) curve of urea formaldehyde and Si modification boron bakelite resin are respectively such as Fig. 2 and Fig. 3 institute
Show.When TGA is tested and heated up, boron bakelite resin can occur further curing reaction and release small molecule, and DTG is bent in corresponding diagram 2
120-470 DEG C of more gentle peak on line.DTG curve is shown in 580-620 DEG C of thermal weight loss rate and thermal weight loss peak occurs in Fig. 2
Value, i.e., the 580-620 DEG C decomposition temperature for maximum thermal weight loss, mainly due to boron bakelite resin, severe thermal is divided in the temperature range
Solution.TGA curve in Fig. 2 can be seen that boron bakelite resin 800 DEG C quality retention rate be 69.9%.
From figure 3, it can be seen that Si modification boron bakelite resin is weightless obvious between 50-100 DEG C, illustrate Si modification boron phenol
The solvent alcohol of urea formaldehyde does not completely remove, may be excessive due to the viscosity of precuring later period Si modification boron bakelite resin, small
Molecules of ethanol is difficult to volatilize.DTG curve is shown in 630-670 DEG C of thermal weight loss rate and thermal weight loss peak value, i.e. 630- occurs in Fig. 3
670 DEG C of decomposition temperatures for maximum thermal weight loss.
Comparing Fig. 2 and Fig. 3 can be seen that the introducing of hetero atom silicon so that the thermal stability of boron bakelite resin improves, and 800 DEG C
Quality retention rate under nitrogen atmosphere is improved from 69.9% to 74.3%；Maximum rhermal decomposition rate is reduced to from 1.14%/min
0.45%/min, and maximum thermal decomposition temperature is improved from 605 DEG C to 640 DEG C.This is because the introducing of silicon is so that boron bakelite resin
The borosilicate heterocycle structure of four sides crosslinking net is presented in molecule, structure is more stable, and heat resistance is more preferable.
The preparation of 2 Si modification boron bakelite resin of embodiment
Prepare boron bakelite resin: first by the phenol 956g of melting using in vacuum mode sucting reaction kettle, while stirring plus
Enter boric acid 155g, is to slowly warm up to 140 DEG C with the rate of 0.7 DEG C/min, is then gradually heated to the rate of 0.1 DEG C/min
164 DEG C, then be gradually heated to 181 DEG C with the rate of 0.2 DEG C/min, control column head temperature is no more than 98 DEG C, collects fraction, when evaporating
Point weight stops heating when reaching 0.2 times of phenol.Fraction is cooled to 60 DEG C, paraformaldehyde 344g is added in two portions, is controlled
Heating rate is 0.1 DEG C/min, is to slowly warm up to 110 DEG C or more, flows back until reaction system comes to life；Flow back 30-
Start decompression dehydration after 40min.Terminate when the gel time of reaction system reaches 50s (200 ± 1 DEG C) and then reacts, ethyl alcohol is added
536g obtains the ethanol solution of boron bakelite resin after dissolution cooling.
It prepares Si modification boron bakelite resin: taking the ethanol solution 100g of boron bakelite resin to be added in reaction kettle, slowly heat up
It is melted completely to 50-60 DEG C, positive isopropyl silicate and each 86g of methyl orthosilicate is added in separatory funnel, in half an hour
It is inside added dropwise, obtains the ethanol solution of Si modification boron bakelite resin within reaction 2.5 hours.
Infrared spectrum, thermal weight loss (TGA) curve and difference quotient thermogravimetric (DTG) curve are similar with 1 result of embodiment, not further
One repeats.
The preparation of 3 Si modification boron bakelite resin of embodiment
Prepare boron bakelite resin: with embodiment 2, when preparing boron bakelite resin, final reaction terminates to discharge immediately, and second is not added
Alcohol to get arrive boron bakelite resin blocks of solid.
It prepares Si modification boron bakelite resin: taking boron bakelite resin solid 70g to be added in reaction kettle, be to slowly warm up to 50-60
It DEG C melts it completely, ethyl orthosilicate 10g, positive isopropyl silicate 30g and methyl orthosilicate 10g is added in separatory funnel,
In being added dropwise in half an hour, Si modification boron bakelite resin is obtained within reaction 4 hours.
Infrared spectrum, thermal weight loss (TGA) curve and difference quotient thermogravimetric (DTG) curve are similar with 1 result of embodiment, not further
One repeats.
The preparation of 4 Si modification boron bakelite resin of embodiment
Prepare boron bakelite resin: with embodiment 2.
It prepares Si modification boron bakelite resin: taking boron bakelite resin solid 70g, crushed and be added in reaction kettle, by positive silicon
Acetoacetic ester 150g and positive isopropyl silicate 50g is added in separatory funnel, in being added dropwise in half an hour, obtains within reaction 3 hours
Si modification boron bakelite resin.
Infrared spectrum, thermal weight loss (TGA) curve and difference quotient thermogravimetric (DTG) curve are similar with 1 result of embodiment, not further
One repeats.
Comparative example 1
Prepare boron bakelite resin: with embodiment 2.
It prepares Si modification boron bakelite resin: taking the ethanol solution 100g of boron bakelite resin to be added in reaction kettle, by positive silicic acid
Ethyl ester 20g is added in separatory funnel, and in being added dropwise in half an hour, reaction obtained the second of Si modification boron bakelite resin after 2 hours
Alcoholic solution, but there is gelatin phenomenon in the ethanol solution of the Si modification boron bakelite resin, there is apparent layering, illustrates dispersibility up to not
To solution requirement, it is not used to performance test.
Comparative example 2
Prepare boron bakelite resin: with embodiment 2.
It prepares Si modification boron bakelite resin: taking the ethanol solution 100g of boron bakelite resin to be added in reaction kettle, by positive silicic acid
Ethyl ester 250g is added in separatory funnel, and in being added dropwise in half an hour, reaction obtained the second of Si modification boron bakelite resin after 2 hours
Alcoholic solution, but the ethanol solution of the Si modification boron bakelite resin precipitates, and has apparent layering, is not homogeneous system, explanation
Solution requirement is not achieved in dispersibility, is not used to performance test.
The preparation of 5 titanium modified boron containing phenolic resin of embodiment
Prepare boron bakelite resin: first by the phenol 956g of melting using in vacuum mode sucting reaction kettle, while stirring plus
Enter boric acid 210g, is to slowly warm up to 140 DEG C with the rate of 0.4 DEG C/min, is then gradually heated to the rate of 0.1 DEG C/min
164 DEG C, then be gradually heated to 181 DEG C with the rate of 0.1 DEG C/min, control column head temperature is no more than 98 DEG C, collects fraction, when evaporating
Point weight stops heating when reaching 0.2 times of phenol, discards fraction, and the resultant product in reaction kettle is boric acid phenol ester.By boron
Acid phenol ester is cooled to 60 DEG C or less；Paraformaldehyde 303g is added in two portions, control heating rate is 0.5 DEG C/min, is slowly risen
Temperature flows back to 110 DEG C or more until reaction system comes to life；Start decompression dehydration after reflux 30-40min.Work as reactant
The gel time of system, which reaches 55s (200 ± 1 DEG C) and then reacts, to be terminated, and ethyl alcohol 536g is added, obtains boron bakelite resin after dissolution cooling
Ethanol solution.
It prepares titanium modified boron containing phenolic resin: taking the ethanol solution 30g of boron bakelite resin to be added in reaction kettle, by butyl titanate
0.3g is slowly added dropwise in reaction kettle, reacts 2 hours at room temperature, and 30g tetrahydrofuran is added, and as solvent, the reaction was continued, until
There is the transparent solution of brownish red to get the THF solution for arriving titanium modified boron containing phenolic resin.
The infrared spectroscopy of resulting titanium modified boron containing phenolic resin is as shown in Figure 8.Fig. 8 shows that titanium accesses boron bakelite resin chain
In, rather than be present in boron bakelite resin system in the form of simple physical blending.1043cm in figure-1(butyl titanate
Methyl stretching vibration peak in 2950cm-1Place, and in the position without obvious absorption peaks in Fig. 8, illustrate that titanium connects with phenol oxygroup
Connect) characteristic absorption peak belong to Ti-O (titanyl ester) key, show that titanium elements have successfully been grafted to boron phenol in the form of chemical bond
In urea formaldehyde.
By the THF solution difference sequencing elevated cure of resulting titanium modified boron containing phenolic resin (when solidification, first by Si modification
Boron bakelite resin solution or titanium modified boron containing phenolic resin solution then heat to 160 DEG C the reaction was continued 2h in 120 DEG C of reaction 2h,
Finally it is warming up to 180 DEG C of reaction 2h.) crush 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.The introducing that can be seen that hetero atom titanium from the TGA curve of Fig. 9 can
To keep the thermal stability of original boron bakelite resin, the quality retention rate under 800 DEG C of nitrogen atmospheres is 68%；DTG curve is shown
There is thermal weight loss peak value, i.e., the 590-630 DEG C decomposition temperature for maximum thermal weight loss in 590-630 DEG C of thermal weight loss rate.
Compare Fig. 2 and Fig. 9 can be seen that titanium modified boron containing phenolic resin rhermal decomposition rate it is suitable with boron bakelite resin, most
Big thermal decomposition temperature is improved from 605 DEG C to 620 DEG C.This is because being introduced into so that four sides is presented in boron bakelite resin molecule for titanium is handed over
The boron titanium heterocycle structure of networking shape, structure is more stable, and heat resistance is more preferable.Although the addition of titanium does not significantly improve boron phenolic tree
The quality retention rate of rouge, 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
(bending angle of titanium modified boron containing phenolic resin is 45 ° or so, and the bending angle of boron bakelite resin is only 160-180 °).Also
It is to say, the addition of titanium significantly improves boron bakelite resin under the premise of the thermal stability for guaranteeing boron bakelite resin does not reduce
Mechanical property.
The preparation of 6 titanium modified boron containing phenolic resin of embodiment
Prepare boron bakelite resin: with embodiment 5.
It prepares titanium modified boron containing phenolic resin: taking boron bakelite resin 50g to be added in reaction kettle, being to slowly warm up to 50-60 DEG C makes
It is melted completely, and 30g tetrahydrofuran is added dropwise and makes it dissolve, slow cooling to room temperature, by tetraethyl titanate 0.5g and isopropyl titanate
0.5g is slowly added dropwise in reaction kettle, reacts 2 hours at room temperature, then 70g tetrahydrofuran is added dropwise the reaction was continued, until there is palm fibre
The solution of red, transparent is to get the THF solution for arriving titanium modified boron containing phenolic resin.
Infrared spectrum, thermal weight loss (TGA) curve, difference quotient thermogravimetric (DTG) curve and bending angle with 5 result class of embodiment
Seemingly, it no longer repeats one by one.
The preparation of 7 titanium modified boron containing phenolic resin of embodiment
Prepare boron bakelite resin: with embodiment 5.
It prepares titanium modified boron containing phenolic resin: taking boron bakelite resin 50g to be added in reaction kettle, being to slowly warm up to 50-60 DEG C makes
It is melted completely, and 30g tetrahydrofuran is added dropwise and makes it dissolve, slow cooling to room temperature, by tetraethyl titanate 0.05g, isopropyl titanate
0.1g and butyl titanate 0.1g are slowly added dropwise in reaction kettle, react 3 hours at room temperature, then 30g tetrahydrofuran and 50g is added dropwise
The reaction was continued for glycol dimethyl ether, until there is the transparent solution of brownish red to get the THF and second of titanium modified boron containing phenolic resin is arrived
Glycol dimethyl ether solution.
Infrared spectrum, thermal weight loss (TGA) curve, difference quotient thermogravimetric (DTG) curve and bending angle with 5 result class of embodiment
Seemingly, it no longer repeats one by one.
The preparation of 8 titanium modified boron containing phenolic resin of embodiment
Prepare boron bakelite resin: with embodiment 5.
It prepares titanium modified boron containing phenolic resin: taking boron bakelite resin 50g to be added in reaction kettle, being to slowly warm up to 50-60 DEG C makes
It is melted completely, and 30g tetrahydrofuran is added dropwise and makes it dissolve, slow cooling to room temperature, by tetraethyl titanate 0.4g and butyl titanate
0.1g is slowly added dropwise in reaction kettle, reacts 3 hours at room temperature, then 85g tetrahydrofuran is added dropwise the reaction was continued, until there is palm fibre
The solution of red, transparent is to get the THF solution for arriving titanium modified boron containing phenolic resin.
Infrared spectrum, thermal weight loss (TGA) curve, difference quotient thermogravimetric (DTG) curve and bending angle with 5 result class of embodiment
Seemingly, it no longer repeats one by one.
Comparative example 3
Prepare boron bakelite resin: with embodiment 5.
It prepares titanium modified boron containing phenolic resin: taking boron bakelite resin 50g to be added in reaction kettle, being to slowly warm up to 50-60 DEG C makes
It is melted completely, and 30g tetrahydrofuran is added dropwise and makes it dissolve, and butyl titanate 0.1g is slowly added dropwise into anti-slow cooling to room temperature
It answers in kettle, reacts 2 hours at room temperature, then 100g glycol dimethyl ether is added dropwise the reaction was continued, until it is transparent brownish red occur
Solution is to get the ethylene glycol dimethyl ether solution for arriving titanium modified boron containing phenolic resin.The thermal stability of the titanium modified boron containing phenolic resin with
Embodiment 5-8 no significant difference, but toughness is more far short of what is expected than embodiment 5-8, slight curvature will fracture, bending angle and implementation
There were significant differences by example 5-8.
Comparative example 4
Prepare boron bakelite resin: with embodiment 5.
It prepares titanium modified boron containing phenolic resin: taking boron bakelite resin 50g to be added in reaction kettle, being to slowly warm up to 50-60 DEG C makes
It is melted completely, and 30g tetrahydrofuran is added dropwise and makes it dissolve, and butyl titanate 2.5g is slowly added dropwise into anti-slow cooling to room temperature
It answers in kettle, reacts 2.5 hours at room temperature, then 90g glycol dimethyl ether is added dropwise the reaction was continued, however brownish red can not be obtained
Transparent solution, reaction system deposited phenomenon are not homogeneous systems, illustrate that dispersibility is not achieved it is obvious that there is apparent layering
Solution requirement, is not used to performance test.
One, dispersibility experiment:
The ethanol solution for the Si modification boron bakelite resin that embodiment 1 and embodiment 2 are obtained, embodiment 5 and embodiment 6
To the THF solution of titanium modified boron containing phenolic resin observed after being placed at room temperature for 3 months, discovery solution is still visibly homogeneous, clarification, thoroughly
Bright, favorable dispersibility is shown in Fig. 4, is from left to right followed successively by embodiment 1, embodiment 2, embodiment 5 and embodiment 6.
The Si modification boron bakelite resin and titanium modified boron containing phenolic resin of comparative example 1 to comparative example 4 are observed, finds modified boron phenol
Either there is gelatin phenomenon in urea formaldehyde, or precipitates, and reaction system has layering, is unable to get 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, inoxidizability is tested:
The antioxygenic property of resin generally uses thermal weight loss (TGA) curve in oxygen atmosphere to be illustrated, and is tested tree
With oxygen thermal degradation reaction occurs for rouge sample under oxygen atmosphere, and the final mass retention rate of resin sample is bigger, inoxidizability
Better.By taking the boron bakelite resin of embodiment 1 and Si modification boron bakelite resin as an example, as shown in fig. 6, boron phenolic tree under oxygen atmosphere
Quality retention rate of the rouge at 800 DEG C is 39.7%；Quality retention rate of the Si modification boron bakelite resin at 800 DEG C be
37.9%, as shown in Figure 7.Illustrate the basic antioxygenic property without changing boron bakelite resin of the addition of silicon atom, can be used as anti-
Ablator uses.
The Si modification boron bakelite resin and titanium modified boron containing phenolic resin of other embodiments are anti-oxidant with boron bakelite resin
Performance is suitable, and no significant difference no longer repeats one by one.
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also the contents of the present invention be should be regarded as.
Claims (1)
1. a kind of preparation method of Si modification boron bakelite resin, which comprises the steps of:
(1) it prepares boron bakelite resin: first the phenol 956g of melting being added while stirring using in vacuum mode sucting reaction kettle
Boric acid 155g is to slowly warm up to 140 DEG C with the rate of 0.7 DEG C/min, is then gradually heated to 164 with the rate of 0.1 DEG C/min
DEG C, then 181 DEG C are gradually heated to the rate of 0.2 DEG C/min, control column head temperature is no more than 98 DEG C, collects fraction, works as fraction
Weight stops heating when reaching 0.2 times of phenol；Fraction is cooled to 60 DEG C, paraformaldehyde 344g is added in two portions, control rises
Warm speed is 0.1 DEG C/min, is to slowly warm up to 110 DEG C or more, flows back until reaction system comes to life；Reflux 30~
Start decompression dehydration after 40min；Terminate when gel time of the reaction system at 200 ± 1 DEG C reaches 50s and then react, second is added
Alcohol 536g obtains the ethanol solution of boron bakelite resin after dissolution cooling；
(2) it prepares Si modification boron bakelite resin: taking the ethanol solution 100g of boron bakelite resin to be added in reaction kettle, be to slowly warm up to
50~60 DEG C melt it completely, positive isopropyl silicate 86g and methyl orthosilicate 86g are added in separatory funnel, in half an hour
It is inside added dropwise, obtains the ethanol solution of Si modification boron bakelite resin within reaction 2.5 hours.
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| 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 |
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