CN104371083A - Technique for synthesizing boron-containing thermoplastic phenol formaldehyde resin by solvothermal process - Google Patents
Technique for synthesizing boron-containing thermoplastic phenol formaldehyde resin by solvothermal process Download PDFInfo
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Abstract
The invention relates to a technique for synthesizing a boron-containing thermoplastic phenol formaldehyde resin by a solvothermal process, which comprises the following steps: adding a thermoplastic phenol formaldehyde resin, a boron-containing compound, oxalic acid and a solvent into a solvothermal reaction kettle, sealing, heating to 120-160 DEG C, keeping the temperature for 0.5-6 hours, cooling to room temperature, and removing the solvent contained in the product, thereby obtaining the boron-containing thermoplastic phenol formaldehyde resin, wherein the boron-containing compound uses an aromatic ring structure as the parent nucleus and hydroxymethyl and boron-containing structure as the substituent group of the aromatic ring structure, and the solvent is water or an alcohol solvent or a mixture of an alcohol solvent and water in a mass ratio of 1:(0.05-0.7). The method has the advantages of high raw material conversion rate and simple technical process; and the obtained product has the advantages of uniform molecular weight distribution and favorable heat resistance. Since the conversion rate of various raw materials is higher, the residual micromolecules do not need to be removed by water washing, thereby effectively reducing the sewage discharge.
Description
Technical field
The present invention relates to a kind of technique of novolak resin, particularly a kind of technique by solvent structure boracic novolac resin.
Technical background
Resol is one of resin of synthetic the earliest, and because raw material is easy to get, synthesis is convenient, has good mechanical property, resistance toheat and outstanding high temperature resistant ablation property, is widely used in the fields such as construction industry, production and aerospace industries.The advantages such as compared to heat-reactive phenolic resin, it is low that novolac resin has free phenol content, and storage period is long, the low and quick solidifying of solidification value.But existing novolac resin is still Shortcomings in the process used, and its main deficiency is embodied in ablation resistance, especially heat decomposition temperature and charring rate still do not meet the demand of application.Therefore, for adapting to the demand of high-technology field, the especially requirement of ablation resistance, modification is carried out to novolac resin very necessary to develop the resol with good heat resistance.
In order to improve the thermotolerance of resol, the elements such as boron, phosphorus, silicon and molybdenum are introduced resol by people, wherein the effect of boron modified phenolic resin the most outstanding (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 contains three kinds: 1. add boron-containing compound (as EP11183-A1 and ZL201210066382.9 etc.) in resol building-up reactions mid-term or later stage.The boron bakelite resin stability in storage that this method obtains is good, but the boron-containing compound added fully and reactive modified phenolic resin, can not directly affect quality and the homogeneity of product.2. boron-containing compound is first generated boric acid phenol ester with phenol reactant, decompression generates containing boron bakelite resin (as RU2318005-C1 and ZL200610024515.0 etc.) with polyformaldehyde reaction after sloughing water again.Although prepared by this method has good thermotolerance containing boron bakelite resin, building-up process is wayward, and the quality of product and homogeneity are subject to the impact of generated time larger.3. first by phenol and formalin or solid formaldehyde water generation reaction poplar alcohol, then generate containing boron bakelite resin with boron-containing compound reaction.The advantage of this method is that quality product easily controls, but still there is boron-containing compound and the insufficient problem of reactive modified phenolic resin.Boron is all incorporated in resol by boric acid ester structure (B-O-C) by aforesaid method, and the structure of products therefrom is as follows:
The subject matter existed in building-up process is: 1. boric acid ester structure, and especially boric acid arylate structural more difficult formation when having water or alcohol, causes Boron contents in resin lower, and the synthesis technique of resin is complicated; 2., in resin synthesis process, the formation of boric acid ester structure can the viscosity of remarkable increase system, even causes resin gel.These deficiencies seriously limit production containing boron bakelite resin and application, and when particularly synthesizing boracic novolac resin (CN201310476899.X), above-mentioned deficiency is more obvious.Therefore, the preparation method developing the boracic novolac resin made new advances is very necessary.
Summary of the invention
The object of the present invention is to provide a kind of technique by solvent structure boracic novolac resin, this technical process is simple, products pure and quantity of wastewater effluent few, obtained boracic novolac resin molecular weight distribution is more homogeneous, softening temperature is controlled, good heat resistance, and has the feature of high charring rate, high boron content and low free part micromolecular compound content.
In order to achieve the above object, the technical solution used in the present invention is in mass parts, the novolac resin of 100 parts, the boron-containing compound of 0.5 ~ 30 part, the oxalic acid of 0.1 ~ 2 part and 5 ~ 100 parts of solvents are joined in solvent thermal reaction still, sealing post-heating is to 120 ~ 160 DEG C, room temperature is cooled to after insulation 0.5 ~ 6h, by the solvent removal in the product that obtains, obtain boracic novolac resin; Wherein, boron-containing compound take aromatic ring structure as parent nucleus, the substituent compound being aromatic ring structure with methylol and boracic structure; Solvent is 1:(0.05 ~ 0.7 by mass ratio) alcoholic solvent and water mix.
Described novolac resin comprises the mixture of one or more arbitrary proportions in random novolac resin, high-ortho novolac resin, bisphenol A-type novolac resin.
Described boracic structure comprise in boron hydroxyl, boric acid ester structure one or both.
Described aromatic ring structure comprises phenyl ring, condensed ring, furans, thiophene, pyrroles or pyridine.
Described boron-containing compound comprises methylol phenylo boric acid, methylol borate ester/monoesters, 4-hydroxymethylpiperidine boric acid, hydroxyl first thienyl boric acid, methylol naphthalene boronic acids or hydroxymethylpyrrol boric acid.
Described alcoholic solvent is the mixture of one or more arbitrary proportions in methyl alcohol, ethanol, propyl alcohol.
By the solvent removal that contains in the product obtained 60 ~ 80 DEG C, dry 1 ~ 6h realizes under-0.02 ~-0.08MPa.
Compared with prior art, beneficial effect of the present invention is:
1, the boron-containing compound that the present invention adopts take aromatic ring structure as parent nucleus, the substituent compound being aromatic ring structure with methylol and boracic structure; This boron-containing compound is adopted to be presoma, the methylol contained in this boron-containing compound and boracic structure all react with the active site on phenol ring in novolac resin and generate stable C-C key, just boron-containing compound introduces novolac resin main chain, meanwhile also B-C key stable in boron-containing compound is introduced in phenol-formaldehyde resin matrix, generate stable boracic novolac resin.
2, contain aromatic ring structure in boron-containing compound of the present invention, the boracic novolac resin synthesized by guarantee has good thermotolerance, avoids introducing fat chain structure simultaneously.In addition, also containing the structural unit that can be transformed into boric acid aryl ester in the curing process in boron-containing compound, to ensure that synthesized boracic novolac resin has good thermostability.
3, owing to containing methylol and boracic structure two class active function groups in the boron-containing compound of the present invention's employing simultaneously, time, under lesser temps (<160 DEG C), the active site of methylol easily and on phenol ring reacts; At higher temperature (>170 DEG C), boracic structure can with phenolic hydroxyl group generation esterification, cause resin gel or solidification.In synthesis containing in the process of boron bakelite resin, the solvent that the present invention adds is water and alcoholic solvent, and under alcohol and water existent condition, only has methylol to react with the active site on phenol ring and can not cause gel or the solidification of novolac resin; Therefore, the solvent that the present invention adds can reduce the generation quantity of boric acid ester structure, to avoid resin generation gel or solidification.Meanwhile, under solvent thermal reaction condition, the existence of solvent reduces the viscosity of reaction system, ensures carrying out smoothly of reaction.
When 4, containing methylol and boron hydroxyl in boron-containing compound of the present invention simultaneously, the larger product of relative molecular mass is generated therebetween owing to can react, its solvability is usually poor, and the present invention adopts solvent-thermal method to prepare boracic novolac resin, it carries out in the solvent thermal reaction still of sealing, that is, the present invention reacts under the condition of heating and pressurizing, significantly can improve the solubility property of the product that methylol and boron hydroxyl generate in boron-containing compound like this, promote that building-up reactions is carried out in the liquid phase.
5, the alcoholic solvent that the present invention selects all can dissolve each other with water, and has lower boiling point and easily remove from synthesized boracic novolac resin at a lower temperature.The molecular size range of mass ratio to boracic novolac resin of water and alcohol has material impact, and when water-content is higher, the boracic novolac resin of lower molecular weight can be separated out from reaction system, affects the further raising of molecular resin amount.When the quality comparation of water in solvent and alcohol is low, acid catalyst cannot demonstrate acidity, the boracic structure simultaneously in boron-containing compound can with alcohol micromolecular generation esterification, generate by product and affect the performance of resin.The molecular weight that can control when boracic novolac resin is separated out from reaction system by regulating the mass ratio of water and alcohol, the boracic novolac resin that synthetic molecular weight size is controlled and molecular weight distribution is homogeneous, and also make softening temperature controlled because synthetic molecular weight size is controlled.
6, the present invention adopts solvent structure boracic novolac resin, the solvent boiling point adopted is low, reaction system internal pressure can be made after more lower boiling solvent is heated to increase, be conducive to the carrying out of building-up reactions, and the transformation efficiency of each product can be improved and reduce the content of free micromolecular compound.And due to free micromolecular compound content remaining in reaction system less, obtained product is pure, therefore reaction only needs desolvation can obtain comparatively pure boracic novolac resin after terminating, do not need further washing and purifying, simplify synthesis technique flow process, and effectively reduce the discharge of waste water.
7, the Boron contents when the content of boron-containing compound is higher in resin is higher, and resin has good thermotolerance, but its cost is higher; When catalyzer oxalic acid content is higher, building-up reactions is very fast, but can affect the performance of boracic novolac resin because catalyst residue is more; The add-on of solvent is relevant with the viscosity of system with the solvability of speed of reaction, novolac resin, when novolac resin there is good solubility and viscosity lower (molecular weight) time the quantity of solvent that adds should be less.Temperature of reaction and time are except being subject to the requirement of product property, also relevant with content with the proportioning of raw material, the composition of solvent, when the content of boron-containing compound in raw material and solvent is higher, temperature of reaction is higher, reaction times is longer, the present invention is by reasonably selecting and proportioning raw material, the control of reaction conditions, while cost-saving, has obtained boracic novolac resin of good performance.
Embodiment
The present invention is comprised the following steps by the technique of solvent structure boracic novolac resin:
In mass parts, the novolac resin of 100 parts, the boron-containing compound of 0.5 ~ 30 part, the oxalic acid of 0.1 ~ 2 part and 5 ~ 100 parts of solvents are joined in solvent thermal reaction still, after stirring, obtains milk-white coloured suspension; Then solvent thermal reaction still is sealed, be heated to 120 ~ 160 DEG C, after insulation 0.5 ~ 6h, be cooled to room temperature, by the product that obtains at 60 ~ 80 DEG C, dry 1 ~ 6h under-0.02 ~-0.08MPa, to remove the solvent contained in product, finally grind, obtain boracic novolac resin.
Solvent thermal reaction still comprises polytetrafluoroethyllining lining and stainless steel kettle, and wherein tetrafluoroethylene should have good sealing property, and stainless steel kettle should be able to bear High Temperature High Pressure.
Novolac resin comprises the mixture of one or more arbitrary proportions in random novolac resin, high-ortho novolac resin, bisphenol A-type novolac resin.Novolac resin is phenols and aldehydes under acidic medium and the excessive condition of phenols through the resin of addition and polycondensation, because phenols is excessive, containing minute quantity or not containing the methylol that reactive behavior is higher in resin, cross-linked network cannot be formed by means of only heating.
Boron-containing compound take aromatic ring structure as parent nucleus, the substituent compound being aromatic ring structure with methylol and boracic structure; The functional group that methylol wherein and boracic structure two class can react with novolac resin.Aromatic ring structure comprises phenyl ring, condensed ring, furans, thiophene, pyrroles or pyridine; Boracic structure comprise in boron hydroxyl, boric acid ester structure one or both; Further, boron-containing compound comprises methylol phenylo boric acid, methylol borate ester/monoesters, 4-hydroxymethylpiperidine boric acid, hydroxyl first thienyl boric acid, methylol naphthalene boronic acids or hydroxymethylpyrrol boric acid.Be further 2-methylol phenylo boric acid monoesters, 5-4-hydroxymethylpiperidine-3-boric acid, 5-hydroxyl first thiophene-2-boric acid, 6-methylol-2-naphthalene boronic acids or 5-methylol-2-pyrrol boronic acid.
The methylol contained in boron-containing compound can react with the active site on phenol ring in novolac resin and generate stable C-C key, by stable C-C key, boron-containing compound is introduced resol main chain, have also been introduced C-B key simultaneously.
The additional proportion of each component is determined according to the performance requriements of resin, and the Boron contents when the content of boron-containing compound is higher in resin is higher, and resin has good thermotolerance, but its cost is higher; When catalyzer oxalic acid content is higher, building-up reactions is very fast, but can affect the performance of boracic novolac resin because catalyst residue is more; The add-on of solvent is relevant with the viscosity of system with the solvability of speed of reaction, novolac resin, when novolac resin there is good solubility and viscosity lower (molecular weight) time the quantity of solvent that adds should be less.Temperature of reaction and time are except by except the requirement of product property, also relevant with content with the proportioning of raw material, the composition of solvent, and when the content of boron-containing compound in raw material and solvent is higher, temperature of reaction is higher, and the reaction times is longer.
Solvent is 1:(0.05 ~ 0.7 by mass ratio) alcoholic solvent and water mix; One or more wherein in the main nail alcohol of alcoholic solvent, ethanol, propyl alcohol.Selected alcoholic solvent should be able to dissolve each other with water, and has lower boiling point and easily remove from synthesized boracic novolac resin at a lower temperature.The molecular size range of mass ratio to boracic novolac resin of water and alcoholic solvent has material impact, and when water-content is higher, the boracic novolac resin of lower molecular weight can be separated out from reaction system, affects the further raising of molecular resin amount.When the quality comparation of water in solvent and alcohol is low, acid catalyst cannot demonstrate acidity, the boracic structure simultaneously in boron-containing compound can with alcohol micromolecular generation esterification, generate by product and affect the performance of resin.The molecular weight that can control when boracic novolac resin is separated out from reaction system by regulating the mass ratio of water and alcohol, the controlled boracic novolac resin homogeneous with molecular weight distribution of synthetic molecular weight size.
The condition of fat desolvation is: temperature 60 ~ 80 DEG C, pressure-0.02 ~-0.08MPa, time 1 ~ 6h.When the solvent in synthetic product is less or after removing completely, boracic structural unit in boracic novolac resin easily and boron hydroxyl or phenolic hydroxyl group can react further under the condition of being heated, generate B-O-B structure or B-O-C structure, cause resin gel or solidification, therefore, should desolvation at a lower temperature.Boron atom pole electron deficiency, is easy to complexing water molecules or alcohol molecule, shows very strong water-absorbent, needs raised temperature, reduces pressure time expand to ensure that water and alcohols remove completely from boracic novolac resin during desolvation.Needing when selecting the condition of desolvation to ensure that solvent removes completely, avoiding product gel or solidification simultaneously.
Compared to the synthetic technology of existing boracic novolac resin, technical process is simple, products pure and the few advantage of quantity of wastewater effluent to adopt the method for solvent structure boracic novolac resin to have, and can be widely used in industrial circle.Compared to existing boracic novolac resin, molecular weight of product distribution is more homogeneous, softening temperature is controlled and the advantage such as good heat resistance to adopt the boracic novolac resin of solvent structure to have, and has a good application prospect.
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1:
It is in the solvent thermal reaction still of 500mL that random for 100g novolac resin, 10g 4-methylol phenylo boric acid and 1g oxalic acid are joined volume, then adds 100g solvent in solvent reaction still, obtains milk-white coloured suspension after stirring; Solvent thermal reaction still is sealed, be incubated 3h under 140 DEG C of conditions after, obtains reaction product.Reduced pressure by solvent thermal reaction still naturally cooling, open reactor after cool to room temperature, obtain the liquid of clear viscous, liquid is light yellow; Obtain white block after above-mentioned pale yellow viscous liquid is dried 4h under 70 DEG C of conditions with-0.08MPa, after grinding, obtain boracic novolac resin; Wherein, solvent is that the dehydrated alcohol of 1:0.11 and deionized water mix by mass ratio.
In synthesized boracic novolac resin, the content of free phenol is 1.31% (volumetry test), and softening temperature 110 DEG C (ring and ball method test), dissolves in ethanol and acetone and other organic solvent.The charring rate of the cured product obtained after gained boracic novolac resin is processed 2h at 220 DEG C be 56.2% (800 DEG C, N
2atmosphere, tube furnace burns 2h), to add the charring rate obtaining product after 5% hexamethylenetetramine processes under the same conditions be 67.4% (800 DEG C, N
2atmosphere, tube furnace burns 2h), far above the cured product of common thermoplastic's resol.
Embodiment 2:
It is in the solvent thermal reaction still of 500mL that 100g high-ortho novolac resin, 20g 2-methylol phenylo boric acid monoesters and 2g oxalic acid are joined volume, then in solvent reaction still, add the solvent of 100g, obtains milk-white coloured suspension after stirring; Solvent thermal reaction still is sealed, be incubated 2h under 160 DEG C of conditions after, obtains reaction product.Reduced pressure by solvent thermal reaction still naturally cooling, open reactor after cool to room temperature, obtain the liquid of clear viscous, liquid is light yellow; Obtain white block after above-mentioned pale yellow viscous liquid is dried 1h under 80 DEG C of conditions with-0.08MPa, after grinding, obtain boracic novolac resin; Wherein, solvent is that the dehydrated alcohol of 1:0.25 and deionized water form by mass ratio.
In synthesized boracic novolac resin, the content of free phenol is 1.03%, and softening temperature 105 DEG C, dissolves in ethanol and acetone and other organic solvent.The charring rate obtaining product after boracic novolac resin and the mixture adding 5% hexamethylenetetramine process 2h at 220 DEG C is respectively 61.4% and 70.8%.The testing method of above-mentioned each index is with embodiment 1.
Embodiment 3:
It is in the solvent thermal reaction still of 500mL that 100g bisphenol A-type novolac resin, 5g 5-4-hydroxymethylpiperidine-3-boric acid and 0.5g oxalic acid are joined volume, then in solvent reaction still, add the solvent of 60g, obtains milk-white coloured suspension after stirring; Solvent thermal reaction still is sealed, be incubated 6h under 120 DEG C of conditions after, obtains reaction product.Reduced pressure by solvent thermal reaction still naturally cooling, open reactor after cool to room temperature, obtain the liquid of clear viscous, liquid is light yellow; Obtain white block after above-mentioned pale yellow viscous liquid is dried 6h under 60 DEG C of conditions with-0.08MPa, after grinding, obtain boracic novolac resin; Wherein, solvent is dehydrated alcohol and the deionized water of the 1:0.7 being by mass ratio.
In synthesized boracic novolac resin, the content of free dihydroxyphenyl propane is 0.27%, and softening temperature 105 DEG C, dissolves in ethanol and acetone and other organic solvent.The charring rate obtaining product after boracic novolac resin and the mixture adding 5% hexamethylenetetramine process 2h at 220 DEG C is respectively 45.8% and 56.6%.The testing method of above-mentioned each index is with embodiment 1.
Embodiment 4:
It is in the solvent thermal reaction still of 500mL that 100g high-ortho novolac resin, 10g 5-hydroxyl first thiophene-2-boric acid and 1g oxalic acid are joined volume, then adds in 100g solvent in solvent reaction still, obtains milk-white coloured suspension after stirring; Solvent thermal reaction still is sealed, be incubated 1h under 160 DEG C of conditions after, obtains reaction product.Reduced pressure by solvent thermal reaction still naturally cooling, open reactor after cool to room temperature, obtain the liquid of clear viscous, liquid is light yellow; Obtain white block after above-mentioned pale yellow viscous liquid is dried 1h under 80 DEG C of conditions with-0.08MPa, after grinding, obtain boracic novolac resin; Wherein, solvent is that the dehydrated alcohol of 1:0.11 and deionized water form by mass ratio.
In synthesized boracic novolac resin, the content of free phenol is 1.45%, and softening temperature 113 DEG C, dissolves in ethanol and acetone and other organic solvent.The charring rate obtaining product after boracic novolac resin and the mixture adding 5% hexamethylenetetramine process 2h at 220 DEG C is respectively 57.6% and 65.3%.The testing method of above-mentioned each index is with embodiment 1.
Embodiment 5:
It is in the solvent thermal reaction still of 500mL that 20g high-ortho novolac resin, the random novolac resin of 80g, 0.5g 6-methylol-2-naphthalene boronic acids and 0.1g oxalic acid are joined volume, in solvent reaction still, add 5g solvent again, after stirring, obtain milk-white coloured suspension; Solvent thermal reaction still is sealed, be incubated 0.5h under 160 DEG C of conditions after, obtains reaction product.Reduced pressure by solvent thermal reaction still naturally cooling, open reactor after cool to room temperature, obtain the liquid of clear viscous, liquid is light yellow; Obtain white block after above-mentioned pale yellow viscous liquid is dried 1h under 80 DEG C of conditions with-0.02MPa, after grinding, obtain boracic novolac resin; Wherein, solvent is that the propyl alcohol of 1:0.05 and deionized water form by mass ratio.
Embodiment 6:
It is in the solvent thermal reaction still of 500mL that random for 100g novolac resin, 0.5g 5-methylol-2-pyrrol boronic acid and 0.1g oxalic acid are joined volume, then adds 30g solvent in solvent reaction still, obtains milk-white coloured suspension after stirring; Solvent thermal reaction still is sealed, be incubated 0.5h under 160 DEG C of conditions after, obtains reaction product.Reduced pressure by solvent thermal reaction still naturally cooling, open reactor after cool to room temperature, obtain the liquid of clear viscous, liquid is light yellow; Obtain white block after above-mentioned pale yellow viscous liquid is dried 1h under 80 DEG C of conditions with-0.05MPa, after grinding, obtain boracic novolac resin; Wherein, solvent is that the alcoholic solvent of 1:0.1 and deionized water form by mass ratio, and alcoholic solvent is the mixed solvent of methyl alcohol and propyl alcohol.
Embodiment 7:
It is in the solvent thermal reaction still of 500mL that random for 100g novolac resin, 0.6g 5-methylol-2-pyrrol boronic acid and 0.2g oxalic acid are joined volume, then in solvent reaction still, add the solvent of 30g, obtains milk-white coloured suspension after stirring; Solvent thermal reaction still is sealed, be incubated 0.5h under 160 DEG C of conditions after, obtains reaction product.Reduced pressure by solvent thermal reaction still naturally cooling, open reactor after cool to room temperature, obtain the liquid of clear viscous, liquid is light yellow; Obtain white block after above-mentioned pale yellow viscous liquid is dried 1h under 80 DEG C of conditions with-0.04MPa, after grinding, obtain boracic novolac resin; Wherein, the first alcohol and water that solvent is 1:0.5 by mass ratio forms.
Boron should be introduced in phenol-formaldehyde resin matrix by stable chemical bond by desirable boracic novolac resin, and avoids occurring gel phenomenon in resin synthesis process.Containing methylol in the boron-containing compound that the present invention adopts, it can be used as presoma to introduce in phenol-formaldehyde resin matrix by stable B-C key by boron in synthesis is containing the process of boron bakelite resin, generate stable boracic novolac resin.Meanwhile, in synthesis containing in the process of boron bakelite resin, add the generation quantity that water or alcohol compound can reduce boric acid ester structure, to avoid resin generation gel.
Solvent-thermal method refers in the pressurized vessel of sealing, with water or other lower boiling organic solvent for medium, and the chemical reaction carried out at high temperature under high pressure.In solvent thermal reaction, solvent can work as a kind of chemical composition and participate in reaction, also can be used as pressure transfer medium simultaneously.Compared to the synthetic method of routine, solvent-thermal method has the following advantages: 1. synthesis device and process are simply, easy control of reaction conditions; 2. the chemical reaction occurred in solvent thermal system carries out faster; 3. in reaction process, temperature of reaction, pressure, treatment time and the composition of medium and the kind of presoma used and concentration all easily control, can by controlling " cutting out " that above-mentioned parameter realizes product property.Based on above-mentioned advantage, solvent-thermal method is widely used for preparing some materials being difficult to be synthesized by ordinary method, as special type is situated between the material of steady structure and condensed state structure.But the application of solvent-thermal method in organic synthesis field is extensive, there is not been reported for the research of synthesizing especially for resol or application.
Problem in the feature of comprehensive solvent thermal reaction and boracic novolac resin building-up process, adopts solvent structure boracic novolac resin to have many advantages.Main manifestations is: 1. at high temperature under high pressure, and the transformation efficiency of speed of reaction and reactant is all higher, decreases the residual quantity of reactant in product; 2. due to the existence of water in reaction process and alcohol, effectively prevent the reaction between phenolic hydroxyl group in novolac resin and boron-containing compound, avoid boracic novolac resin, in building-up process, gel phenomenon occurs; 3. the viscosity of reaction system is lower, is conducive to the high softening-point novolac resin that synthetic molecular weight is larger; 4. by controlling organic solvent and the ratio of water in solvent, can control the relative molecular mass of resol, the product that molecular weight is larger is easily separated out and no longer participates in reacting in mixed solvent, contributes to synthetic molecular weight and to distribute homogeneous resol; 5. hydro-thermal reaction is carried out in airtight container, can effectively avoid the oxygen in air to the oxidation of resol.
When containing methylol and boracic structure two class active function groups in boron-containing compound simultaneously, under lesser temps (<160 DEG C), the active site of methylol easily and on phenol ring reacts; At higher temperature (>170 DEG C), boracic structure can with phenolic hydroxyl group generation esterification, cause resin gel or solidification.When adopting boron-containing compound synthesis boracic novolac resin, need to control reaction conditions and only make methylol and the raw alkylated reaction of phenol environment-development, and avoid the formation of boric acid ester structure and make resin system generation gel.When there is alcohol and water in synthetic system, effectively can reduce the probability that boron hydroxyl and phenolic hydroxyl group react, avoiding resin gel in building-up process.Therefore, the solvent-thermal method being solvent with water and/or alcohol can prepare the boracic novolac resin with superperformance.In addition, when containing methylol and boron hydroxyl in boron-containing compound simultaneously, the larger product of relative molecular mass is generated therebetween owing to can react, its solvability is usually poor, but its solubility property significantly improves under the condition of heating and pressurizing, can promote that building-up reactions is carried out in the liquid phase.
In sum, the mixture adopting water and/or alcohol is solvent, can be synthesized the boracic novolac resin with good over-all properties by solvent-thermal method.Compare the synthetic method of existing boracic novolac resin, of the present invention have innovative and novelty significantly by solvent structure boracic novolac resin.Meanwhile, because various raw-material level of response is higher, synthesized boracic novolac resin does not need through follow-up water washing process, can simplify the synthesis technique flow process of resol, and effectively reduces the discharge of waste water.Therefore, solvent structure boracic novolac resin is adopted to have suitability.
Claims (7)
1. the technique by solvent structure boracic novolac resin, it is characterized in that: in mass parts, the novolac resin of 100 parts, the boron-containing compound of 0.5 ~ 30 part, the oxalic acid of 0.1 ~ 2 part and 5 ~ 100 parts of solvents are joined in solvent thermal reaction still, sealing post-heating is to 120 ~ 160 DEG C, room temperature is cooled to after insulation 0.5 ~ 6h, by the solvent removal in the product that obtains, obtain boracic novolac resin; Wherein, boron-containing compound take aromatic ring structure as parent nucleus, the substituent compound being aromatic ring structure with methylol and boracic structure; Solvent is 1:(0.05 ~ 0.7 by mass ratio) alcoholic solvent and water mix.
2. the technique by solvent structure boracic novolac resin according to claim 1, is characterized in that: described novolac resin comprises the mixture of one or more arbitrary proportions in random novolac resin, high-ortho novolac resin, bisphenol A-type novolac resin.
3. the technique by solvent structure boracic novolac resin according to claim 1, is characterized in that: described boracic structure comprise in boron hydroxyl, boric acid ester structure one or both.
4. the technique by solvent structure boracic novolac resin according to claim 3, is characterized in that: described aromatic ring structure comprises phenyl ring, condensed ring, furans, thiophene, pyrroles or pyridine.
5. the technique by solvent structure boracic novolac resin according to claim 1 or 3, is characterized in that: described boron-containing compound comprises methylol phenylo boric acid, methylol borate ester/monoesters, 4-hydroxymethylpiperidine boric acid, hydroxyl first thienyl boric acid, methylol naphthalene boronic acids or hydroxymethylpyrrol boric acid.
6. the technique by solvent structure boracic novolac resin according to claim 1, is characterized in that: described alcoholic solvent is the mixture of one or more arbitrary proportions in methyl alcohol, ethanol, propyl alcohol.
7. the technique by solvent structure boracic novolac resin according to claim 1, is characterized in that: by the solvent removal contained in the product obtained 60 ~ 80 DEG C, dry 1 ~ 6h realizes under-0.02 ~-0.08MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750064A (en) * | 2016-11-11 | 2017-05-31 | 西安交通大学 | A kind of preparation method of phenolic resin renewable at room temperature and its recovery process and application |
| CN110144046A (en) * | 2019-05-28 | 2019-08-20 | 沙县宏盛塑料有限公司 | A kind of preparation method of boracic phenolic resin microspheres and carbosphere |
| CN115403898A (en) * | 2022-09-30 | 2022-11-29 | 西安交通大学 | Phenolic resin suitable for RTM (resin transfer molding) process and preparation method and application thereof |
| CN115467050A (en) * | 2022-08-25 | 2022-12-13 | 广西大学 | Preparation method of boron-modified wood liquefied carbon fiber spinning solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289033A (en) * | 2013-04-08 | 2013-09-11 | 西安交通大学 | Aryl boron-containing phenolic resin and preparation method thereof |
| CN103554395A (en) * | 2013-10-12 | 2014-02-05 | 西安交通大学 | Preparation method of aryl-containing boron thermoplastic phenolic resin |
-
2014
- 2014-11-11 CN CN201410632423.5A patent/CN104371083B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289033A (en) * | 2013-04-08 | 2013-09-11 | 西安交通大学 | Aryl boron-containing phenolic resin and preparation method thereof |
| CN103554395A (en) * | 2013-10-12 | 2014-02-05 | 西安交通大学 | Preparation method of aryl-containing boron thermoplastic phenolic resin |
Non-Patent Citations (1)
| Title |
|---|
| SHUJUAN WANG ET AL: "Synthesis and characterization of novel phenolic resins containing aryl-boron backbone and their utilization in polymeric composites with improved thermal and mechanical properties", 《POLYM. ADV. TECHNOL》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750064A (en) * | 2016-11-11 | 2017-05-31 | 西安交通大学 | A kind of preparation method of phenolic resin renewable at room temperature and its recovery process and application |
| CN106750064B (en) * | 2016-11-11 | 2021-04-20 | 西安交通大学 | Preparation method of room-temperature renewable phenolic resin and recovery process and application thereof |
| CN110144046A (en) * | 2019-05-28 | 2019-08-20 | 沙县宏盛塑料有限公司 | A kind of preparation method of boracic phenolic resin microspheres and carbosphere |
| 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 |
| CN115403898A (en) * | 2022-09-30 | 2022-11-29 | 西安交通大学 | Phenolic resin suitable for RTM (resin transfer molding) process and preparation method and application thereof |
| 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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