CN104371083B - A kind of technique by solvent structure boracic thermoplastic phenolic resin - Google Patents
A kind of technique by solvent structure boracic thermoplastic phenolic resin Download PDFInfo
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Abstract
A kind of technique by solvent structure boracic thermoplastic phenolic resin, thermoplastic phenolic resin, boron-containing compound, oxalic acid and solvent are added in solvent thermal reaction kettle, 120~160 DEG C are heated to after sealing, room temperature is cooled to after 0.5~6h of insulation, the solvent removal contained in the product that will be obtained, obtains boracic thermoplastic phenolic resin；Wherein, boron-containing compound is the compound of the substitution base with methylol and boracic structure as aromatic ring structure with aromatic ring structure as parent nucleus；Solvent uses water, alcohols solvent or is 1 by mass ratio：The alcohols solvent and water of (0.05~0.7) are mixed.The present invention has feed stock conversion high and the simple advantage of technological process using the method for solvent structure boracic thermoplastic phenolic resin, and resulting molecular weight of product distribution is homogeneous, heat-resist.Because the conversion ratio of all kinds of raw material is higher, do not need to remove remaining small molecule by washing, can effectively reduce the discharge of sewage.
Description
Technical field
It is more particularly to a kind of to pass through solvent structure boracic thermoplastic the present invention relates to a kind of technique of novolak resin
The technique of property phenolic resin.
Technical background
Phenolic resin is one of resin artificial synthesized earliest, and because raw material is easy to get, synthesis is convenient, with good machinery
The high temperature resistant ablation property of performance, heat resistance and protrusion, is widely used in construction industry, manufacturing industry and aerospace industries etc.
Field.Compared to thermosetting phenolic resin, thermoplastic phenolic resin has free phenol content low, and storage period is long, and solidification temperature is low
And the advantages of quick solidifying.But, existing thermoplastic phenolic resin still suffers from deficiency during use, its main deficiency body
Present ablation resistance, especially heat decomposition temperature and charring rate are still unsatisfactory for the demand of application.Therefore, it is adaptation new and high technology
The requirement of the demand in field, especially ablation resistance, is modified to develop with good heat-resisting to thermoplastic phenolic resin
The phenolic resin of property is very necessary.
In order to improve the heat resistance of phenolic resin, the elements such as boron, phosphorus, silicon and molybdenum are introduced phenolic resin, wherein boron by people
The effect of phenol-formaldehyde resin modified the most prominent (Abdalla MO, et al.Polymer.2003, (44):7353-7359；Jing
XL,et al.Carbon.2007,45(10):1965-1971).The synthetic method of current boron bakelite resin mainly has three kinds：①
Boron-containing compound (such as EP11183-A1 and ZL201210066382.9) is added in phenolic resin synthetic reaction mid-term or later stage.
The boron bakelite resin storage stability that this method is obtained is good, but the boron-containing compound for adding can not be fully anti-with phenolic resin
Should, directly affect the quality and uniformity of product.2. boron-containing compound is first generated into boric acid phenol ester with phenol reactant, decompression is de-
(such as RU2318005-C1 and ZL200610024515.0) containing boron bakelite resin is generated after removing water with polyformaldehyde reaction again.Though
What so prepared by this method has good heat resistance containing boron bakelite resin, but building-up process is whard to control, the quality of product
Influenceed larger by generated time with uniformity.3. first by phenol and formalin or solid formaldehyde reaction generation saligenin,
Contain boron bakelite resin with boron-containing compound reaction generation again.The advantage of the method is that product quality is easily controlled, but still is existed
Boron-containing compound and the insufficient problem of reactive modified phenolic resin.The above method is introduced boron by boric acid ester structure (B-O-C)
To in phenolic resin, the structure of products therefrom is as follows：
Subject matter present in building-up process is：1. boric acid ester structure, especially boric acid arylate structural have water or
More difficult formation during alcohol, Boron contents are relatively low in causing resin, and the synthesis technique of resin is complicated；2. in resin synthesis process, boron
The formation of acrylate structure can dramatically increase the viscosity of system, even result in resin gel.These deficiencies seriously limit boracic
The production and application of phenolic resin, it is above-mentioned when particularly synthesizing boracic thermoplastic phenolic resin (CN201310476899.X)
It is not enough more obvious.Therefore, the preparation method for developing new boracic thermoplastic phenolic resin is very necessary.
The content of the invention
It is an object of the invention to provide a kind of technique by solvent structure boracic thermoplastic phenolic resin, the work
Skill flow is simple, products pure and quantity of wastewater effluent are few, and obtained boracic thermoplastic phenolic resin molecular weight distribution is more uniform, soft
Change point controllable, heat-resist, and the characteristics of with charring rate high, high boron content and low free part micromolecular compound content.
In order to achieve the above object, the technical solution adopted by the present invention is in terms of mass parts, by 100 parts of thermoplastic phenolic
Resin, 0.5~30 part of boron-containing compound, 0.1~2 part of oxalic acid and 5~100 parts of solvents are added in solvent thermal reaction kettle,
120~160 DEG C are heated to after sealing, room temperature is cooled to after 0.5~6h of insulation, the solvent removal in the product that will be obtained is obtained
Boracic thermoplastic phenolic resin；Wherein, boron-containing compound is with aromatic ring structure as parent nucleus, with methylol and boracic structure as aromatic ring
The compound of the substitution base of structure；Solvent is 1 by mass ratio：The alcohols solvent and water of (0.05~0.7) are mixed.
Described thermoplastic phenolic resin includes random thermoplastic phenolic resin, high-ortho novolac resin, bisphenol-A
The mixture of one or more arbitrary proportion in type thermoplastic phenolic resin.
Described boracic structure include boron hydroxyl, boric acid ester structure in one or two.
Described aromatic ring structure includes phenyl ring, condensed ring, furans, thiophene, pyrroles or pyridine.
Described boron-containing compound include methylol phenyl boric acid, methylol borate ester/monoesters, hydroxymethylpyridine boric acid,
Hydroxyl first thienyl boric acid, methylol naphthalene boronic acids or hydroxymethylpyrrol boric acid.
Described alcohols solvent is the mixture of one or more arbitrary proportion in methyl alcohol, ethanol, propyl alcohol.
The solvent removal contained in the product that will be obtained is that 1~6h realities are dried under 60~80 DEG C, -0.02~-0.08MPa
Existing.
Compared with prior art, the beneficial effects of the present invention are：
1st, it, with aromatic ring structure as parent nucleus, is aromatic ring knot with methylol and boracic structure that the boron-containing compound that the present invention is used is
The compound of the substitution base of structure；It is presoma to use the boron-containing compound, the methylol and boracic contained in the boron-containing compound
Structure all reacts the C-C keys of generation stabilization, just boron-containing compound with the active site on phenol ring in thermoplastic phenolic resin
Thermoplastic phenolic resin main chain is introduced, the B-C keys that at the same time will also stablize in boron-containing compound are introduced into phenol-formaldehyde resin matrix,
Generate the boracic thermoplastic phenolic resin of stabilization.
2nd, aromatic ring structure is contained in boron-containing compound of the present invention, it is ensured that synthesized boracic thermoplastic phenolic resin has good
Good heat resistance, while avoiding introducing fat chain structure.In addition, also contain in boron-containing compound to be transformed into the curing process
It is the construction unit of boric acid aryl ester, there is good heat endurance with the boracic thermoplastic phenolic resin for ensureing synthesized.
3rd, methylol and the class active function groups of boracic structure two are contained simultaneously in the boron-containing compound used due to the present invention
When, lower temperature (<160 DEG C) under, methylol easily reacts with the active site on phenol ring；Temperature higher (>170
DEG C) under, boracic structure can occur esterification with phenolic hydroxyl group, cause resin gel or solidification.Contain boron bakelite resin in synthesis
During, the solvent that the present invention is added is water and alcohols solvent, and under conditions of alcohol and water presence, only methylol can be with
Gel or solidification that active site on phenol ring is reacted without causing thermoplastic phenolic resin；Therefore, the solvent that the present invention is added
The generation quantity of boric acid ester structure can be reduced, gel or solidification occur to avoid resin.Meanwhile, in solvent thermal reaction condition
Under, the presence of solvent reduces the viscosity of reaction system, it is ensured that reaction is smoothed out.
When the 4th, containing methylol and boron hydroxyl simultaneously in boron-containing compound of the present invention, due to can react therebetween
The larger product of generation relative molecular mass, its dissolubility is generally poor, and the present invention prepares boracic thermoplastic using solvent-thermal method
Property phenolic resin, its be sealing solvent thermal reaction kettle in carry out, that is to say, that the present invention be heating pressurize condition
Lower reaction, can so significantly improve the solubility property of methylol and the product of boron hydroxyl generation in boron-containing compound, promote to close
Carried out in the liquid phase into reaction.
5th, the alcohols solvent of present invention selection all enough dissolves each other with water energy, and with relatively low boiling point easily compared with low temperature
Removed from synthesized boracic thermoplastic phenolic resin under degree.Water divides boracic thermoplastic phenolic resin with the mass ratio of alcohol
Son amount size has material impact, and when water content is higher, the boracic thermoplastic phenolic resin of lower molecular weight can be from reaction
Separated out in system, influence the further raising of molecular resin amount.When the mass ratio of solvent reclaimed water and alcohol is relatively low, acid catalyst
Acidity cannot be shown, while the boracic structure in boron-containing compound can occur esterification with alcohol micromolecular, by-product is generated
Thing and influence the performance of resin.By adjusting water boracic thermoplastic phenolic resin from reaction system can be controlled with the mass ratio of alcohol
Molecular weight during middle precipitation, synthetic molecular weight size is controllable and the homogeneous boracic thermoplastic phenolic resin of molecular weight distribution, and by
It is controllable also so that softening point is controllable in synthetic molecular weight size.
6th, the present invention uses solvent structure boracic thermoplastic phenolic resin, and the solvent boiling point for being used is low, compared with low boiling
The solvent of point can make pressure increase in reaction system after being heated, be conducive to the carrying out of synthetic reaction, and can improve turning for each product
Rate and reduce the content of free micromolecular compound.And due in reaction system remaining free micromolecular compound content compared with
Desolvation is only needed to can obtain more pure boracic thermoplastic phenolic after few, obtained product is pure, therefore reaction terminates
Resin, it is not necessary to further washing and purifying, simplifies synthesis technique flow, and effectively reduce the discharge of waste water.
7th, the Boron contents when the content of boron-containing compound is higher in resin are higher, and resin has good heat resistance, but
Its is relatively costly；Synthetic reaction is very fast when catalyst oxalic acid content is higher, but can influence boracic heat because catalyst residual is more
The performance of plastic phenolic resin；The addition of solvent and the viscosity of reaction rate, the dissolubility of thermoplastic phenolic resin and system
Relevant, the quantity of solvent added when thermoplastic phenolic resin has good dissolubility and viscosity relatively low (molecular weight is smaller) should be compared with
It is few.Reaction temperature and time, the composition and content of proportioning, solvent also with raw material were relevant in addition to the requirement by product property,
When the content of boron-containing compound in raw material and solvent is higher, reaction temperature is higher, and the reaction time is more long, and the present invention is by original
The rational selection of material and proportioning, the control of reaction condition while cost-effective, have been obtained boracic thermoplasticity of good performance
Phenolic resin.
Specific embodiment
The present invention is comprised the following steps by the technique of solvent structure boracic thermoplastic phenolic resin：
In terms of mass parts, by 100 parts of thermoplastic phenolic resin, 0.5~30 part of boron-containing compound, 0.1~2 part of grass
Acid and 5~100 parts of solvents are added in solvent thermal reaction kettle, and milk-white coloured suspension is obtained after stirring；Then by solvent thermal reaction
Kettle is sealed, and is heated to 120~160 DEG C, and room temperature is cooled to after 0.5~6h of insulation, the product that will be obtained 60~80 DEG C, -0.02
1~6h is dried under~-0.08MPa, to remove the solvent contained in product, is finally ground, obtain boracic thermoplastic phenolic resin.
Solvent thermal reaction kettle includes polytetrafluoroethyllining lining and stainless steel kettle, and wherein polytetrafluoroethylene (PTFE) should have good
Sealing property, stainless steel kettle should be able to bear HTHP.
Thermoplastic phenolic resin includes random thermoplastic phenolic resin, high-ortho novolac resin, bisphenol A-type thermoplastic
The mixture of one or more arbitrary proportion in property phenolic resin.Thermoplastic phenolic resin is phenols and aldehydes in acid medium
With under conditions of phenols excess through addition and the resin of polycondensation, due to phenols excess, containing very small amount or being free of in resin
Reactivity methylol higher, only cannot form cross-linked network by heating.
Boron-containing compound is the change of the substitution base with methylol and boracic structure as aromatic ring structure with aromatic ring structure as parent nucleus
Compound；The functional group that methylol therein and the class of boracic structure two can react with thermoplastic phenolic resin.Aromatic ring structure
Including phenyl ring, condensed ring, furans, thiophene, pyrroles or pyridine；Boracic structure includes the one kind or two in boron hydroxyl, boric acid ester structure
Kind；Further, boron-containing compound includes methylol phenyl boric acid, methylol borate ester/monoesters, hydroxymethylpyridine boric acid, hydroxyl first
Thienyl boric acid, methylol naphthalene boronic acids or hydroxymethylpyrrol boric acid.Further it is 2- methylol phenyl boric acids monoesters, 5- methylol pyrroles
Pyridine -3- boric acid, 5- hydroxyl first thiophene -2- boric acid, 6- methylol -2- naphthalene boronic acids or 5- methylol -2- pyrrol boronic acids.
The methylol contained in boron-containing compound can react life with the active site on phenol ring in thermoplastic phenolic resin
Into the C-C keys of stabilization, boron-containing compound is introduced by phenolic resin main chain by the C-C keys of stabilization, while have also been introduced C-B keys.
The additional proportion of each component determines according to the performance requirement of resin, when the content of boron-containing compound is higher in resin
Boron contents it is higher, resin has good heat resistance, but its is relatively costly；When catalyst oxalic acid content is higher synthetic reaction compared with
Hurry up, but the performance of boracic thermoplastic phenolic resin can be influenceed because catalyst residual is more；The addition and reaction rate of solvent,
The dissolubility of thermoplastic phenolic resin is relevant with the viscosity of system, when thermoplastic phenolic resin has good dissolubility and viscosity
The quantity of solvent added when relatively low (molecular weight is smaller) should be less.Reaction temperature and time in addition to the requirement by product property, go back
The composition and content of proportioning, solvent with raw material are relevant, and temperature is reacted when the content of boron-containing compound in raw material and solvent is higher
Degree is higher, and the reaction time is more long.
Solvent is 1 by mass ratio：The alcohols solvent and water of (0.05~0.7) are mixed；Wherein alcohols solvent is referred mainly to
One or more in methyl alcohol, ethanol, propyl alcohol.Selected alcohols solvent should be able to be miscible with water, and with relatively low boiling point
And easily removed from synthesized boracic thermoplastic phenolic resin at a lower temperature.The mass ratio of water and alcohols solvent is to boracic
The molecular size range of thermoplastic phenolic resin has material impact, when water content is higher, the boracic thermoplasticity of lower molecular weight
Phenolic resin can be separated out from reaction system, influence the further raising of molecular resin amount.When solvent reclaimed water and the quality of alcohol
Than it is relatively low when, acid catalyst cannot show acidity, while the boracic structure in boron-containing compound can be sent out with alcohol micromolecular
Raw esterification, generates accessory substance and influences the performance of resin.By adjusting water boracic thermoplastic can be controlled with the mass ratio of alcohol
Property molecular weight of phenolic resin when being separated out from reaction system, synthetic molecular weight size is controllable and the homogeneous boracic of molecular weight distribution
Thermoplastic phenolic resin.
The condition of fat desolvation is：60~80 DEG C of temperature, pressure -0.02~-0.08MPa, 1~6h of time.Work as synthesis
Solvent in product is less or after removing completely, boracic construction unit in boracic thermoplastic phenolic resin easily with boron hydroxyl
Or phenolic hydroxyl group can further react under conditions of being heated, B-O-B structures or B-O-C structures are generated, cause resin gel
Or solidification, therefore, should desolvation at a lower temperature.Boron atom pole electron deficient, it is easy to be complexed hydrone or alcohol molecule, table
Reveal very strong water imbibition, a liter high-temperature is needed during desolvation, pressure is reduced and to extend the time complete to ensure water and alcohols
Removed from boracic thermoplastic phenolic resin.Need to ensure that solvent is removed completely when the condition of desolvation is selected, while keeping away
Exempt from product gel or solidification.
Compared to the synthetic technology of existing boracic thermoplastic phenolic resin, using solvent structure boracic thermoplasticity phenol
The method of urea formaldehyde has the advantages that simple technological process, products pure and quantity of wastewater effluent are few, can be widely applied to industry
Field.Compared to existing boracic thermoplastic phenolic resin, the boracic thermoplastic phenolic resin using solvent structure has
Molecular weight of product is distributed the advantages such as more uniform, softening point is controllable and heat-resist, has a good application prospect.
With reference to embodiment, the invention will be further described：
Embodiment 1：
The random thermoplastic phenolic resins of 100g, 10g 4- methylols phenyl boric acids and 1g oxalic acid are added to volume for 500mL
Solvent thermal reaction kettle in, then in solvent reaction kettle add 100g solvents, milk-white coloured suspension is obtained after stirring；By solvent heat
Reactor is sealed, and product is obtained after being incubated 3h under the conditions of 140 DEG C.By the decompression of solvent thermal reaction kettle natural cooling, cooling
Reactor is opened after to room temperature, the liquid of clear viscous is obtained, liquid is in light yellow；By above-mentioned pale yellow viscous liquid at 70 DEG C
White block is obtained after drying 4h with conditions of -0.08MPa, it is polished to obtain boracic thermoplastic phenolic resin；Wherein, it is molten
Agent is 1 by mass ratio:0.11 absolute ethyl alcohol and deionized water is mixed.
The content of free phenol is 1.31% (titration test), softening point in synthesized boracic thermoplastic phenolic resin
110 DEG C (ring and ball method test), in dissolving in ethanol and acetone and other organic solvent.By gained boracic thermoplastic phenolic resin 220
The charring rate that the cured product obtained after 2h is processed at DEG C is 56.2% (800 DEG C, N2Atmosphere, tube furnace burns 2h), add 5% 6
Methine tetramine obtains product charring rate after processing under the same conditions is 67.4% (800 DEG C, N2Atmosphere, tube furnace burns
2h), far above the cured product of common thermoplastic's phenolic resin.
Embodiment 2：
100g high-ortho novolac resins, 20g 2- methylol phenyl boric acid monoesters and 2g oxalic acid are added into volume is
In the solvent thermal reaction kettle of 500mL, then to the solvent of 100g is added in solvent reaction kettle, milk-white coloured suspension is obtained after stirring；
By the sealing of solvent thermal reaction kettle, product is obtained after being incubated 2h under the conditions of 160 DEG C.Solvent thermal reaction kettle natural cooling is subtracted
Pressure, reactor is opened after being cooled to room temperature, obtains the liquid of clear viscous, and liquid is in light yellow；By above-mentioned thick pale yellow liquid
Body obtains white block after drying 1h under conditions of 80 DEG C and -0.08MPa, polished to obtain boracic thermoplastic phenolic resin
Fat；Wherein, solvent be by mass ratio be 1:0.25 absolute ethyl alcohol and deionized water composition.
The content of free phenol is 1.03% in synthesized boracic thermoplastic phenolic resin, and 105 DEG C of softening point dissolves in second
In alcohol and acetone and other organic solvent.The mixture of 5% hexamethylenetetramine of boracic thermoplastic phenolic resin and addition is at 220 DEG C
The charring rate that product is obtained after treatment 2h is respectively 61.4% and 70.8%.The method of testing of above-mentioned each index is with embodiment 1.
Embodiment 3：
100g bisphenol A-types thermoplastic phenolic resin, 5g 5- hydroxymethylpyridine -3- boric acid and 0.5g oxalic acid are added to body
During product is for the solvent thermal reaction kettle of 500mL, then to the solvent of 60g is added in solvent reaction kettle, milky suspension is obtained after stirring
Liquid；By the sealing of solvent thermal reaction kettle, product is obtained after being incubated 6h under the conditions of 120 DEG C.Solvent thermal reaction kettle is naturally cold
But depressurize, reactor is opened after being cooled to room temperature, obtain the liquid of clear viscous, liquid is in light yellow；Will be above-mentioned light yellow viscous
Thick liquid obtains white block after drying 6h under conditions of 60 DEG C and -0.08MPa, polished to obtain boracic thermoplastic phenolic
Resin；Wherein, solvent is be 1 by mass ratio:0.7 absolute ethyl alcohol and deionized water.
The content of free bisphenol-A is 0.27% in synthesized boracic thermoplastic phenolic resin, and 105 DEG C of softening point is solvable
In ethanol and acetone and other organic solvent.The mixture of 5% hexamethylenetetramine of boracic thermoplastic phenolic resin and addition is 220
The charring rate for obtaining product at DEG C after treatment 2h is respectively 45.8% and 56.6%.The same embodiment of method of testing of above-mentioned each index
1。
Embodiment 4：
100g high-ortho novolac resins, 10g 5- hydroxyl first thiophene -2- boric acid and 1g oxalic acid are added into volume is
In the solvent thermal reaction kettle of 500mL, then in solvent reaction kettle add 100g solvents in, milk-white coloured suspension is obtained after stirring；
By the sealing of solvent thermal reaction kettle, product is obtained after being incubated 1h under the conditions of 160 DEG C.Solvent thermal reaction kettle natural cooling is subtracted
Pressure, reactor is opened after being cooled to room temperature, obtains the liquid of clear viscous, and liquid is in light yellow；By above-mentioned thick pale yellow liquid
Body obtains white block after drying 1h under conditions of 80 DEG C and -0.08MPa, polished to obtain boracic thermoplastic phenolic resin
Fat；Wherein, solvent be by mass ratio be 1:0.11 absolute ethyl alcohol and deionized water composition.
The content of free phenol is 1.45% in synthesized boracic thermoplastic phenolic resin, and 113 DEG C of softening point dissolves in second
In alcohol and acetone and other organic solvent.The mixture of 5% hexamethylenetetramine of boracic thermoplastic phenolic resin and addition is at 220 DEG C
The charring rate that product is obtained after treatment 2h is respectively 57.6% and 65.3%.The method of testing of above-mentioned each index is with embodiment 1.
Embodiment 5：
By 20g high-ortho novolac resins, the random thermoplastic phenolic resins of 80g, 0.5g 6- methylol -2- naphthalene boron
Acid and 0.1g oxalic acid are added in the solvent thermal reaction kettle that volume is 500mL, then to 5g solvents are added in solvent reaction kettle, are stirred
After obtain milk-white coloured suspension；By the sealing of solvent thermal reaction kettle, product is obtained after being incubated 0.5h under the conditions of 160 DEG C.Will
Solvent thermal reaction kettle natural cooling is depressurized, and reactor is opened after being cooled to room temperature, obtains the liquid of clear viscous, and liquid is in pale yellow
Color；White block is obtained after above-mentioned pale yellow viscous liquid is dried into 1h under conditions of 80 DEG C and -0.02MPa, it is polished
Obtain boracic thermoplastic phenolic resin；Wherein, solvent be by mass ratio be 1:0.05 propyl alcohol and deionized water composition.
Embodiment 6：
The random thermoplastic phenolic resins of 100g, 0.5g 5- methylol -2- pyrrol boronic acids and 0.1g oxalic acid are added to volume
In for the solvent thermal reaction kettle of 500mL, then to 30g solvents are added in solvent reaction kettle, milk-white coloured suspension is obtained after stirring；Will
Solvent thermal reaction kettle is sealed, and product is obtained after being incubated 0.5h under the conditions of 160 DEG C.Solvent thermal reaction kettle natural cooling is subtracted
Pressure, reactor is opened after being cooled to room temperature, obtains the liquid of clear viscous, and liquid is in light yellow；By above-mentioned thick pale yellow liquid
Body obtains white block after drying 1h under conditions of 80 DEG C and -0.05MPa, polished to obtain boracic thermoplastic phenolic resin
Fat；Wherein, solvent be by mass ratio be 1:0.1 alcohols solvent and deionized water composition, and alcohols solvent is methyl alcohol and propyl alcohol
Mixed solvent.
Embodiment 7：
The random thermoplastic phenolic resins of 100g, 0.6g 5- methylol -2- pyrrol boronic acids and 0.2g oxalic acid are added to volume
In for the solvent thermal reaction kettle of 500mL, then to the solvent of 30g is added in solvent reaction kettle, milk-white coloured suspension is obtained after stirring；
By the sealing of solvent thermal reaction kettle, product is obtained after being incubated 0.5h under the conditions of 160 DEG C.By solvent thermal reaction kettle natural cooling
Decompression, reactor is opened after being cooled to room temperature, obtains the liquid of clear viscous, and liquid is in light yellow；By above-mentioned thick pale yellow
Liquid obtains white block after drying 1h under conditions of 80 DEG C and -0.04MPa, polished to obtain boracic thermoplastic phenolic resin
Fat；Wherein, solvent be by mass ratio be 1：0.5 first alcohol and water composition.
Should be introduced into boron in phenol-formaldehyde resin matrix by the chemical bond of stabilization by preferable boracic thermoplastic phenolic resin, and be kept away
Exempt from occur gel phenomenon in resin synthesis process.Contain methylol in the boron-containing compound that the present invention is used, as
Can be introduced into boron in phenol-formaldehyde resin matrix by the B-C keys of stabilization during synthesis is containing boron bakelite resin by presoma, raw
Into the boracic thermoplastic phenolic resin of stabilization.Meanwhile, during synthesis is containing boron bakelite resin, add water or alcohol compound
The generation quantity of boric acid ester structure can be reduced, gel occurs to avoid resin.
Solvent-thermal method refers in the pressure vessel of sealing, with water or other lower boiling organic solvents as medium, in height
The chemical reaction carried out under warm high pressure.In solvent thermal reaction, solvent can work as a kind of chemical constituent and participate in anti-
Should, can be used as pressure transmission medium.Compared to conventional synthetic method, solvent-thermal method has advantages below：1. synthesize
Equipment and process are simple, easy control of reaction conditions；2. the chemical reaction for occurring in solvent hot system carries out faster；3. it is anti-
The composition of reaction temperature, pressure, process time and medium and the species and concentration of presoma used are easily controlled during answering
System, can be realized " cutting out " to product property by controlling above-mentioned parameter.Based on above-mentioned advantage, solvent-thermal method is widely used for
Prepare some materials for being difficult to synthesize by conventional method, the material of such as extraordinary be situated between steady structure and condensed state structure.But, solvent
Hot method is not extensive in the application of organic synthesis field, and the particularly research or application for phenolic resin synthesis not yet appears in the newspapers
Road.
Problem in the characteristics of comprehensive solvent thermal reaction and boracic thermoplastic phenolic resin building-up process, using solvent-thermal method
Synthesis boracic thermoplastic phenolic resin has many advantages.It is mainly shown as：1. at high temperature under high pressure, reaction rate and reactant
Conversion ratio it is higher, reduce the residual quantity of reactant in product；2. due to the presence of course of reaction reclaimed water and alcohol, effectively resistance
The reaction between the phenolic hydroxyl group and boron-containing compound in thermoplastic phenolic resin is stopped, it is to avoid boracic thermoplastic phenolic resin is being closed
There is gel phenomenon during；3. the viscosity of reaction system is relatively low, is conducive to the high softening-point heat that synthetic molecular weight is larger
Plastic phenolic resin；4. by controlling the ratio of organic solvent and water in solvent, the average molecular matter of phenolic resin can be controlled
Amount, the larger product of molecular weight is easily separated out in mixed solvent and is no longer participate in reaction, contributes to synthetic molecular weight to be distributed equal
One phenolic resin；5. hydro-thermal reaction is carried out in closed container, can be prevented effectively from the oxygen in air to phenolic resin
Oxidation.
When in boron-containing compound simultaneously contain two class active function groups of methylol and boracic structure when, lower temperature (<
160 DEG C) under, methylol easily reacts with the active site on phenol ring；Temperature higher (>170 DEG C) under, boracic structure can
There is esterification with phenolic hydroxyl group, cause resin gel or solidification.Boracic thermoplastic phenolic resin is synthesized using boron-containing compound
, it is necessary to control the reaction condition only to make methylol and phenol ring that alkylated reaction occurs during fat, and avoid the formation of boric acid ester structure and make
There is gel in resin system.When there is alcohol and water in synthetic system, the probability of boron hydroxyl and phenolic hydroxyl group reaction can be effectively reduced,
Avoid resin gel in building-up process.Therefore, the solvent-thermal method with water and/or alcohol as solvent can be prepared with superperformance
Boracic thermoplastic phenolic resin.Additionally, when methylol and boron hydroxyl is contained simultaneously in boron-containing compound, due to therebetween
Can react and generate the larger product of relative molecular mass, its dissolubility is generally poor, but under conditions of pressurization is heated
Its solubility property is significantly improved, and synthetic reaction can be promoted to carry out in the liquid phase.
In sum, the mixture for using water and/or alcohol is solvent, can be synthesized with good comprehensive by solvent-thermal method
The boracic thermoplastic phenolic resin of performance.Compared to the synthetic method of existing boracic thermoplastic phenolic resin, the present invention is used
There is significant innovative and novelty by solvent structure boracic thermoplastic phenolic resin.Simultaneously as various originals
The extent of reaction of material is higher, and synthesized boracic thermoplastic phenolic resin needs not move through follow-up water-washing process, can simplify
The synthesis technique flow of phenolic resin, and effectively reduce the discharge of waste water.Therefore, using solvent structure boracic thermoplasticity phenol
Urea formaldehyde has applicability.
Claims (5)
1. a kind of technique by solvent structure boracic thermoplastic phenolic resin, it is characterised in that：In terms of mass parts, will
100 parts of thermoplastic phenolic resin, 0.5~30 part of boron-containing compound, 0.1~2 part of oxalic acid and 5~100 parts of solvents are added
120~160 DEG C are heated to in solvent thermal reaction kettle, after sealing, room temperature is cooled to after 0.5~6h of insulation, the product that will be obtained
In solvent removal, obtain boracic thermoplastic phenolic resin；Wherein, boron-containing compound is with aromatic ring structure as parent nucleus, with hydroxyl first
Base and boracic structure are the compound of the substitution base of aromatic ring structure；Solvent is 1 by mass ratio：The alcohols solvent of (0.05~0.7)
Mixed with water；
Described boron-containing compound includes methylol phenyl boric acid, methylol borate ester, hydroxymethylpyridine boric acid, hydroxyl first thiophene boron
Acid, methylol naphthalene boronic acids or hydroxymethylpyrrol boric acid；
Under conditions of alcohol and water presence, only methylol can be with the work on phenol ring in thermoplastic phenolic resin in boron-containing compound
Property point react generation stabilization C-C keys, gel or the solidification of thermoplastic phenolic resin will not be caused, by stabilization C-C
Boron-containing compound is introduced thermoplastic phenolic resin main chain by key, while have also been introduced C-B keys, generates the boracic thermoplasticity phenol of stabilization
Urea formaldehyde.
2. the technique by solvent structure boracic thermoplastic phenolic resin according to claim 1, it is characterised in that：
Described thermoplastic phenolic resin includes random thermoplastic phenolic resin, high-ortho novolac resin, bisphenol A-type thermoplasticity
The mixture of one or more arbitrary proportion in phenolic resin.
3. the technique by solvent structure boracic thermoplastic phenolic resin according to claim 1, it is characterised in that：
Described aromatic ring structure includes phenyl ring, thiophene, pyrroles or pyridine.
4. the technique by solvent structure boracic thermoplastic phenolic resin according to claim 1, it is characterised in that：
Described alcohols solvent is the mixture of one or more arbitrary proportion in methyl alcohol, ethanol, propyl alcohol.
5. the technique by solvent structure boracic thermoplastic phenolic resin according to claim 1, it is characterised in that：
The solvent removal contained in the product that will be obtained is to dry 1~6h under 60~80 DEG C, -0.02~-0.08MPa to realize.
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| CN110144046B (en) * | 2019-05-28 | 2021-05-28 | 沙县宏盛塑料有限公司 | Boron-containing phenolic resin microspheres and preparation method of carbon microspheres |
| CN115467050A (en) * | 2022-08-25 | 2022-12-13 | 广西大学 | Preparation method of boron-modified wood liquefied carbon fiber spinning solution |
| CN115403898B (en) * | 2022-09-30 | 2023-12-19 | 西安交通大学 | Phenolic resin suitable for RTM process and preparation method and application thereof |
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| Synthesis and characterization of novel phenolic resins containing aryl-boron backbone and their utilization in polymeric composites with improved thermal and mechanical properties;Shujuan Wang et al;《Polym. Adv. Technol》;20131106(第25期);152-159 * |
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