CN101805435B - Preparation method of boron modified phenolic resin - Google Patents
Preparation method of boron modified phenolic resin Download PDFInfo
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- CN101805435B CN101805435B CN 201010152008 CN201010152008A CN101805435B CN 101805435 B CN101805435 B CN 101805435B CN 201010152008 CN201010152008 CN 201010152008 CN 201010152008 A CN201010152008 A CN 201010152008A CN 101805435 B CN101805435 B CN 101805435B
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Abstract
The invention discloses a preparation method of boron modified phenolic resin, which comprises the following steps that: (1) phenol and formaldehyde in the molar ratio of 1.0:0.1 to 1.0 is added into a reactor, to be stirred under acid environment and reflux for 5 to 6 hours; (2) a reaction product prepared in step (1) is distilled and hydrated at normal pressure, until the water content is less than 10 weight percent; (3) the produce dehydrated in step (2) is added with a compound which contains boron hydroxyl, to have esterification; and the input of the compound which contains boron hydroxyl is 20 weight percent of that of the phenol at most. The synthesis method provided by the invention is simple and feasible, the prepared resin has stable performance and is beneficial to large-scale industrial production, and the prepared boron modified phenolic resin has excellent thermal oxidation and ablation resistant performance, and can be widely applied to high-temperature brake materials, ablation resistant materials, heat insulation materials and other fields.
Description
Technical field
The present invention relates to a kind of preparation method of resol, especially a kind of preparation method of boron modified phenolic resin.
Background technology
Resol, owing to have excellent mechanical property, resistance toheat, ablation resistance, electrical insulation properties, dimensional stability, forming process and flame retardant properties, its making raw material is easy to get simultaneously, cheap, production technique and equipment are simple, have become the indispensable material of industrial sector.But along with industrial expansion, the particularly development of space flight and aviation and other national defence sophisticated technologies, the shortcoming such as traditional unmodified resol has occurred still that fragility is large, poor toughness and thermotolerance are low, thus limited the development of its high performance material.In order to adapt to the development need of automotive industry, aerospace and national defense industry, must carry out modification to resol, improving its thermotolerance and toughness is the important developing direction of resol.
In order to use to a greater extent resol, people have carried out a large amount of study on the modification to resol, strive overcoming its existing defective, improve its performance, satisfy the needs of hi-tech development.So have the nonmetal properties-correcting agent such as the silicon of employing, boron that resol is processed, and obtained good progress.With the matrix material of Effect of Organosilicon-modified Phenol-formaldehyde Resin preparation, can under 200 ℃～260 ℃ conditions, work the long duration, and can be used as instantaneous high temperature material, as the ablator of rocket, guided missile etc.In the molecular structure of resol, introduce inorganic boron, can make the thermotolerance of the resol of boron modification, instantaneous high thermal resistance, ablation resistance, mechanical property is also much better than common resol, their as much are used for the fields of space technology such as rocket, guided missile and space vehicle, as good ablation resistant material.
At present the most frequently used boron improves the resol method, is to utilize boric acid and phenol reactant to generate phenyl-borate, again with Paraformaldehyde 96 or formalin reaction, generates the resol of boracic.The boron modified phenolic resin heatproof oxidation performance is good, introduced in the boron phenolic aldehyde molecular structure in addition flexible larger-the B-O-key, toughness and mechanical property also increase.The three-dimensional crosslinking structure of boracic in the cured product makes its ablation resistance and anti-neutron radiation performance be better than general resol.The flexural strength of the carbon cloth boron phenolic laminate that the employing boron modified phenolic resin makes reaches 420MPa, and shearing resistance is up to 39.7MPa; The oxy-acetylene mass ablative rate is 0.0364g/s only, than carbon/barium phenolic materials low 20%.
Chinese patent 200610024515.0 provides a kind of preparation method of high boron content modified phenolic resins, but the prepared resin of this invention is thermosetting resin, the production control difficulty is controlled improper meeting and is solidified in reactor, is difficult to realize large-scale industrial production.
Summary of the invention
The present invention is directed to deficiency, propose a kind of preparation method of boron modified phenolic resin, simple and easy to control, be beneficial to large-scale commercial production.
In order to realize the foregoing invention purpose, the invention provides following technical scheme: a kind of preparation method of boron modified phenolic resin may further comprise the steps:
(1), to add mol ratio in the reactor be 1.0: 0.1～1.0 phenol and aldehyde, the stirring and refluxing reaction is 5 hours～6 hours under sour environment;
(2), the reaction product of step (1) carries out the air distillation dehydration, to water content less than 10 % by weight;
(3), add the boracic oxy-compound in the product after step (2) dehydration, carry out esterification; The charging capacity of described boracic oxy-compound mostly is 20 % by weight of phenol most.
Preferably, in the step (1), in reactor, add phenol first, under sour environment, stir, and then drip aldehyde.
Preferably, in the step (1), the mol ratio of phenolic aldehyde is 1.0: 0.5～0.9.
Preferably, in the step (2), water content is less than 5%.
Preferably, in the step (2), water content is less than 2%.
Preferably, in the step (3), described boracic oxy-compound is boric acid, boric anhydride.
Preferably, in the step (3), the charging capacity of described boracic oxy-compound mostly is 10 % by weight of phenol most.
Preferably, the resulting carboxylate of step (3) is carried out decompression dehydration, water content is less than 10%.
Preferably, in the step (1), described sour environment is for to add acidic solution in reactor.The mineral acids such as example hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, tosic acid, or organic acid.
Compared with prior art, the present invention adopts traditional synthetic method to prepare resol, and under sour environment, making the synthetic resol that obtains is linear structure, is novolac resin with the term restriction of reaction.In synthetic novolac resin, add the boracic oxy-compound, carry out esterification and obtain the thermoplasticity boron modified phenolic resin.Whole preparation process, reaction conditions is gentle, is very suitable for industrial production and uses.For the ease of the control reaction process, can also under sour environment, add first phenol, and then add aldehyde.
Synthetic method provided by the invention is simple, the resin property that obtains is stable, be beneficial to large-scale industrial production, the gained boron modified phenolic resin has good thermal oxidation resistance performance, ablation resistance, can be widely used in the fields such as high-temperature brake material, ablation resistant material, thermal insulation material.
Embodiment
A kind of preparation method of boron modified phenolic resin may further comprise the steps:
(1), to add mol ratio in the reactor be 1.0: 0.1～1.0 phenol and aldehyde, the stirring and refluxing reaction is 5 hours～6 hours under sour environment;
(2), the reaction product of step (1) carries out the air distillation dehydration, to water content less than 10 % by weight;
(3), add the boracic oxy-compound in the product after step (2) dehydration, carry out esterification; The charging capacity of described boracic oxy-compound mostly is 20 % by weight of phenol most.
The preparation method of above-mentioned boron modified phenolic resin, at first adopt traditional synthetic method to prepare resol, term restriction that just will reaction is under sour environment, namely in reactor, added acidic solution, thereby making the synthetic resol that obtains is linear structure, is novolac resin.First this novolac resin is dewatered, to water content less than 10 % by weight, if moisture is higher than 10% follow-up esterification of impact; In synthetic novolac resin, add the boracic oxy-compound at last, carry out esterification and obtain the thermoplasticity boron modified phenolic resin; The charging capacity of boracic oxy-compound mostly is 20 % by weight of phenol most, otherwise can cause the viscosity of reaction system to increase, and reaction is difficult to carry out.Whole preparation process, reaction conditions is gentle, is very suitable for industrial production and uses.For the ease of the control reaction process, can also under sour environment, add first phenol, and then add aldehyde.
Both are used for not special restriction of phenol of the present invention and aldehyde, as long as can form the resol monomer; Wherein phenol is generally selected phenol, cresols, xylenol, Resorcinol, nonylphenol, cardanol etc. or its mixture, and aldehyde is generally selected formaldehyde, acetaldehyde, furfural, Paraformaldehyde 96 etc.Because the most important with the phenol formaldehyde resin that phenol and formaldehyde are synthetic, its output accounts for the first place of phenolic resinoid, to use also the most extensively, the embodiment of the invention is example with regard to the phenol formaldehyde resin that adopts phenol and formaldehyde to synthesize.
Below in conjunction with embodiment, further set forth the present invention:
Embodiment 1:
With phenol 500g, 37% formalin 301g, oxalic acid 5g puts into thermometer, whipping appts, in the 1000ml reaction vessel of reflux exchanger, heat to 80 ℃～85 ℃ constant temperature 1 hour, and then be warmed up to 90 ℃～95 ℃, constant temperature 1 hour, be warmed up at last 100 ℃, back flow reaction 3 hours, finish reaction and carry out the air distillation dehydration, air distillation is dewatered to 150 ℃～160 ℃, detects when moisture content is 2.3% in the resin, stops air distillation, add boric acid 50g, esterification 30 minutes is then at 150 ℃～160 ℃, under the condition of pressure 8000Pa, the underpressure distillation dehydration, dephenolize, when the detection moisture content is 4.3%, stop underpressure distillation, emit the material cooling, get 530g boron modified phenolic resin A.
Embodiment 2:
With phenol 445g, the sulfuric acid 4.45g of content 20% puts into thermometer, whipping appts, in the 1000ml reaction vessel of reflux exchanger, heat to 80 ℃～90 ℃, begin to drip formaldehyde, added in 90 minutes, and then be warmed up to 100 ℃, back flow reaction 3 hours, add the hydrated barta neutralization, finish reaction and carry out the air distillation dehydration, air distillation is dewatered to 160 ℃～170 ℃, when the detection moisture content is 1.2%, stop air distillation, add boric acid 66g, esterification 40 minutes is then at 160 ℃～170 ℃, underpressure distillation dehydration under the condition of pressure 5000Pa, dephenolize, when the detection moisture content is 3.7%, stop underpressure distillation, emit the material cooling, get 408g boron modified phenolic resin B.
Embodiment 3:
With phenol 325g, cardanol 16g, 37% formalin 182g, 10% hydrochloric acid 0.5g puts into thermometer, whipping appts, in the 1000ml reaction vessel of reflux exchanger, heat to 80 ℃～90 ℃, Paraformaldehyde 96 20 grams of adding 92%, about 40 minutes of 80-90 ℃ of reaction of control temperature, then at the Paraformaldehyde 96 that adds 20 grams 92%, about 30 minutes of 80 ℃～90 ℃ reactions, at the Paraformaldehyde 96 that adds remaining 33.1 grams 92%, 85 ℃～95 ℃ reactions 30 minutes, be warmed up at last 100 ℃, constant temperature 4 hours finishes reaction and carries out the air distillation dehydration, be dewatered to 140 ℃～150 ℃ of temperature of charge, detect moisture content and reach 2.7%, stop air distillation, then add boric acid 32.5g, esterification 50 minutes, then at 160 ℃～170 ℃, underpressure distillation dehydration under the condition of pressure 7000Pa, dephenolize when detecting moisture content 3.2%, stops underpressure distillation, emit the material cooling, get 323g boron modified phenolic resin C.
Embodiment 4
With phenol 400g, cresols 100 grams, 37% formalin 345g, content 40% phosphoric acid 5g puts into has thermometer, whipping appts, in the 1000ml reaction vessel of reflux exchanger, heat to 70 ℃～80 ℃, about 1 hour of isothermal reaction, then be warmed up to 90 ℃～95 ℃, about 30 minutes of isothermal reaction, be warmed up at last 100 ℃, back flow reaction 4 hours finishes reaction and carries out air distillation, distillation to 150 ℃～160 ℃, when detecting moisture content 2.2%, stop air distillation, add 40 gram boric anhydrides and carry out esterification, 150 ℃～160 ℃ esterifications 50 minutes, then at 150 ℃～160 ℃, under the condition of pressure 8000Pa, the underpressure distillation dehydration, dephenolize is when detecting moisture content 4.3%, emit the material cooling, get 515g boron modified phenolic resin D.
Embodiment 5:
With phenol 400g, nonyl phenol 100 grams, 37% formalin 301g, oxalic acid 5g puts into thermometer, whipping appts, in the 1000ml reaction vessel of reflux exchanger, heat to 80 ℃～85 ℃ constant temperature 1 hour, and then be warmed up to 90 ℃～95 ℃, constant temperature 1 hour, be warmed up at last 100 ℃, back flow reaction 3 hours finishes reaction and carries out the air distillation dehydration, and air distillation is dewatered to 150-160 ℃, detect when moisture content is 2.2% in the resin, stop air distillation, add boric acid 50g, esterification 30 minutes, then at 150 ℃～160 ℃, under the condition of pressure 8000Pa, the underpressure distillation dehydration, dephenolize when the detection moisture content is 3.9%, stops underpressure distillation, emit the material cooling, get 535g boron modified phenolic resin E.
Comparing embodiment 1
With phenol 282 grams, boric acid 62 grams, 400 milliliters of toluene join with thermometer, whipping appts, in the 1000ml reaction vessel of reflux exchanger, intensification boiling reflux reaction 3 hours, Paraformaldehyde 96 102 grams of adding 92%, 90 ℃ were reacted 3 hours, then decompression dehydration, along with the liquid that carries out in the reaction flask that dewaters becomes sticky thick gradually, reaction is 3 hours～4 hours under 90 ℃～100 ℃ reduced pressure, when it is yellow-green colour, when the polymerization time when detecting 150 ℃ is 60 seconds～70 seconds, from reaction flask, emit fast the material cooling, get 317 gram thermoset boron modified phenolic resin F.
Comparing embodiment 2:
Phenol 500g, 37% formalin 345g, oxalic acid 5g put into have thermometer, in the 1000ml reaction vessel of whipping appts, reflux exchanger, heat to 80 ℃～90 ℃, constant temperature 1 hour, be warmed up at last 100 ℃, back flow reaction 3 hours finishes reaction and carries out the air distillation dehydration, and distillation is to 150 ℃～160 ℃, the blowing cooling gets 515g resol G.
Product performance detect
Get respectively product 1 gram that above-described embodiment obtains, be placed on the iron plate that is heated to 180 ℃, heated 5 minutes, if resin is the viscosity flow state, then resin is thermoplastic resin; If gel state, then resin is thermosetting resin.
Detected result sees the following form
As can be seen from the above table, embodiment 1,2,3,4,5 product are the thermoplasticity boron modified phenolic resin, and the product of comparing embodiment 1 is the thermoset boron modified phenolic resin, does not carry out modification and the product of comparing embodiment 2 adds boron compound; The heating energy of thermoset boron modified phenolic resin own solidifies, under the condition of blowing temperature, can be cured reaction, so the reaction end blowing must be rapidly, can not in reaction unit, stop, otherwise the resin index can great changes will take place, seriously will cause solidifying in reactor, therefore in order to reduce the blowing time, can only produce in the smaller conversion unit of capacity, this controlling of production process difficulty is large, is unfavorable for suitability for industrialized production.Curing reaction self does not occur in thermoplasticity boron modified resin under the condition of heating, technology controlling and process is simple, can produce in main equipment, is conducive to a large amount of suitability for industrialized production, and product performance are stable.
Carbon residue test process and condition:
Take by weighing respectively above-described embodiment product 10g, add the 1g hexamethylenetetramine, put into pulverizer and pulverized 40 seconds.
Take by weighing the resin that 2g crushes, move in the crucible, in 150 ℃ baking oven, solidified 2 hours.
The crucible that fills cured resin is put into 800 ℃ muffle furnace, cover crucible cover, roast took out crucible after 7 minutes from muffle furnace, the calculating carbon residue of weighing.
Table carbon residue analytical results
As can be seen from the table, the carbon residue of the resol of thermoplasticity boron modification is compared with the carbon residue of the unmodified resol of comparing embodiment 2, and content is obviously higher; the introducing of boron is described; generated-the B-O-key, protected phenolic hydroxyl group, increased thermotolerance and the oxidation resistent susceptibility of resin.
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. the preparation method of a boron modified phenolic resin may further comprise the steps:
⑴, to add mol ratio in the reactor be 1.0: 0.1～1.0 phenol and aldehyde, and the stirring and refluxing reaction is 5 hours～6 hours under sour environment, obtains linear phenolic resin;
⑵ the reaction product of, step ⑴ is carried out air distillation dehydration, to water content less than 10 % by weight;
⑶ add boric acid or boric anhydride in, the product after the step ⑵ dehydration, carry out esterification; The charging capacity of described boric acid or boric anhydride mostly is 20 % by weight of phenol most.
2. preparation method according to claim 1 is characterized in that: among the step ⑴, add phenol first in reactor, stir under sour environment, and then drip aldehyde.
3. preparation method according to claim 1, it is characterized in that: among the step ⑴, the mol ratio of phenolic aldehyde is 1.0: 0.5～0.9.
4. preparation method according to claim 1, it is characterized in that: among the step ⑵, water content is less than 5%.
5. according to claim 1 or 4 described preparation methods, it is characterized in that: among the step ⑵, water content is less than 2%.
6. preparation method according to claim 1, it is characterized in that: among the step ⑶, the charging capacity of described boric acid or boric anhydride mostly is 10 % by weight of phenol most.
7. preparation method according to claim 1, it is characterized in that: the resulting carboxylate of step ⑶ is carried out decompression dehydration, and water content is less than 10%.
8. preparation method according to claim 1, it is characterized in that: among the step ⑴, described sour environment is for to add acidic solution in reactor.
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| CN104629253A (en) * | 2015-03-03 | 2015-05-20 | 山东圣泉新材料股份有限公司 | Phenolic resin composition and application thereof |
| CN105315419B (en) * | 2015-11-26 | 2017-07-28 | 西北工业大学 | A kind of preparation method of the boron modification of resistance to ablation thermoplastic phenolic resin |
| CN105418868B (en) * | 2015-12-10 | 2017-07-25 | 山东圣泉新材料股份有限公司 | Boron modified phenolic resin, preparation method and friction material |
| CN106317354B (en) * | 2016-08-30 | 2018-11-06 | 山东莱芜润达新材料有限公司 | Thermostable phenolic resin and preparation method thereof |
| CN106883363B (en) * | 2017-03-09 | 2019-03-08 | 中国科学院化学研究所 | A kind of boron hydridization addition curable phenolic resin and its preparation method and application |
| CN107082859A (en) * | 2017-05-12 | 2017-08-22 | 浙江杭摩合成材料股份有限公司 | A kind of preparation method of the heat resistance modified phenolic resin of toughness reinforcing |
| CN108428920A (en) * | 2018-03-30 | 2018-08-21 | 王敏 | A kind of preparation method of high temperature resistant type electrolyte |
| CN111423549A (en) * | 2020-05-22 | 2020-07-17 | 安徽凯沃科技有限公司 | Boron phenolic resin compositely modified by cashew nut shell oil and organic silicon and preparation method thereof |
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