CN103833946A - Preparation method of phenolic resin - Google Patents
Preparation method of phenolic resin Download PDFInfo
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- CN103833946A CN103833946A CN201410072382.9A CN201410072382A CN103833946A CN 103833946 A CN103833946 A CN 103833946A CN 201410072382 A CN201410072382 A CN 201410072382A CN 103833946 A CN103833946 A CN 103833946A
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Abstract
The invention provides a preparation method of phenolic resin. The preparation method comprises the following steps of under the action of an alkaline catalyst, carrying out first reaction on phenolic compounds, aldehyde compounds, a reducing agent and boron-containing compounds to obtain reaction mixture, then carrying out second reaction on the reaction mixture and nitrogen-containing compound to obtain phenolic resin. The preparation method provided by the invention has the advantages that the chromaticity change of the prepared phenolic resin is small in different storage periods before curing and after finish of the curing process, the original performance of the resin is also not influenced and the usability of the resin is improved.
Description
Technical field
The invention belongs to technical field of polymer materials, relate in particular to a kind of preparation method of resol.
Background technology
Resol is the general designation of the resin that generates of reacting under the condition that exists at catalyzer of phenols and aldehydes, it is the macromolecular material of suitability for industrialized production the earliest, resol after solidifying has good physics, chemical property, is widely used in all respects such as industry, agricultural, national defence and national economy.
Resol is often used to make moulding compound material, friction materials, refractory materials, laminating material etc., the moulding compound of being prepared by resol, because it has remarkable heat-resisting, insulation and mechanical property, especially good dimensional stability, uses extensively at aspects such as space flight and aviation, naval vessel and ship for civil use, firearms, electronics and electrical component, power equipment components.
Resol is divided into heat-reactive phenolic resin and novolac resin conventionally, and novolac resin is generally acid catalyzed solid resin form and exists, and heat-reactive phenolic resin is generally the liquid resin form existence of base catalysis.This wherein heat-reactive phenolic resin there is very strong wetting capacity, processability is good, volume density is large, void content is low, dimensional stabilizing and heat-resisting, fire-retardant, corrosion-resistant, electrical insulation capability is good, thereby be widely used in industry-by-industry.
Along with science and technology and economic fast development, downstream industry increases day by day to the demand of heat-reactive phenolic resin, simultaneously more and more stricter to the requirement of its each side.But owing to containing a large amount of phenolic hydroxyl groups in resol, in the process storing at resol, the especially heat-reactive phenolic resin of liquid, is easy to be oxidized to quinones substance, causes color of resin to redden; More serious, in resin hot setting process, because contact oxygen is more, phenolic hydroxyl group is more prone to be oxidized to quinones, and the time is longer, and temperature is higher, and the color after solidifying is darker.And in use, along with the prolongation of time, color of resin can deepen because of oxidation.These shortcomings all serious restriction resol of light color or product colour is required to the application of the association areas such as high and persistence is good at ask for something.
In prior art, after producer adopts terpolycyantoamino-formaldehyde resin, urea-formaldehyde resin, benzene emulsion, ACRYLIC EMULSION etc. to solidify in the industry, light-colored material replaces heat-reactive phenolic resin, but because the terpolycyantoamino-formaldehyde resin shelf lives is too short, product fragility is large; On The Water Resistance of Urea-formaldehyde Resin, weathering resistance are poor; Emulsion toughness is large, intensity is little, without rigid, restricted the range of application of product, and if resol is carried out modification or carries out arbitrary proportion blend by terpolycyantoamino-formaldehyde resin, urea-formaldehyde resin, emulsion, the color of resol still cannot be improved, as long as a small amount of resol just can make resin solidification darken, if add antioxidant, because they do not participate in the reaction of phenolic aldehyde, the performance of resin can be affected, thereby has affected the application of resol.
Therefore, how to find a kind of method can make heat-reactive phenolic resin after shelf lives and solidification process complete before solidifying, reduce the degree of color burn, the stability of maintenance color, do not affect again its performance, be resol manufacturer problem demanding prompt solution simultaneously always.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of resol, after heat cured resol prepared by preparation method provided by the invention different shelf lives and solidification process before solidifying complete, the colourity of resin changes less, do not affect again the original performance of resin, improved the operability of resin simultaneously.
The preparation method who the invention discloses a kind of resol, comprises the following steps:
A) under the effect of basic catalyst, phenolic compound, aldehyde compound, reductive agent and boron-containing compound are carried out to the first reaction, obtain reaction mixture;
B) by above-mentioned steps A) reaction mixture and the nitrogenous compound that obtain carry out second and react, and obtains resol.
Preferably, described basic catalyst is one or more in alkalimetal oxide, alkali metal hydroxide, aminated compounds, ammoniacal liquor and strong base-weak acid salt.
Preferably, described reductive agent is one or more in ferrous sulfate, POTASSIUM BOROHYDRIDE, sodium borohydride, boron oxide, lithium aluminum hydride, S-WAT and tin protochloride.
Preferably, described boron-containing compound is sodium tetraborate, sodium metaborate, boric acid, high boron lime borate, lime borate, barium metaborate, calcium metaborate, one or more in colemanite and metaboric acid.
Preferably, described nitrogenous compound is one or more in diethanolamine, urea, trimeric cyanamide, dimethylethanolamine, trolamine, hydrazine, quadrol, ammonium sulfate and ammonium chloride.
Preferably, described phenolic compound is one or more in phenol, cresols, dimethyl phenol, nonylphenol, dihydroxyphenyl propane, Resorcinol, propylphenol and ethylphenol; Described aldehyde compound is formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or trioxymethylene.
Preferably, the mol ratio of described phenolic compound and aldehyde compound is 1:(0.1～3.5); Described basic catalyst and phenolic compound mass ratio are (0.001～0.3): 1.
Preferably, the total mass of described boron-containing compound, reductive agent and nitrogenous compound and the mass ratio of phenolic compound are (0.01～0.3): 1; The mass ratio of described boron-containing compound, reductive agent and nitrogenous compound is 1:(0.1～0.8): (0.5～2.0).
Preferably, the temperature of described the first reaction is 60～80 DEG C, and the temperature of described the second reaction is 80～90 DEG C.
Preferably, described steps A) be specially:
A1) under the effect of basic catalyst, phenolic compound, aldehyde compound and reductive agent are carried out to pre-reaction, obtain pre-reaction mixture;
A2) pre-reaction mixture and the boron-containing compound that above-mentioned steps are obtained react, and obtain reaction mixture;
The temperature of described pre-reaction is 60～70 DEG C, and the temperature of described reaction is 70～80 DEG C.
The invention provides a kind of preparation method of novolac epoxy, under the effect of basic catalyst, phenolic compound, aldehyde compound, reductive agent and boron-containing compound are carried out to the first reaction, obtain reaction mixture; By above-mentioned steps A) reaction mixture and the nitrogenous compound that obtain carry out second and react, and obtains resol.Compared with prior art; the present invention is in phenol-formaldehyde reaction process; the boron-containing compound of specified proportion, reductibility compound and nitrogenous compound are joined in reaction process according to distinctive order; boron-containing compound, reductibility compound, nitrogenous compound three participate in respectively phenolic aldehyde polycondensation and interact, and have effectively protected phenolic hydroxyl group not oxidized one-tenth quinones in the synthetic and curing whole process of resol.Thereby along with variation and the solidification process in storage time of resol, the colourity of resol prepared by the present invention changes less, has effectively solved the impact of storage time on color of resin, has extended the duration of service of resin, has improved the operability of resin.Experimental result shows, light heat-reactive phenolic resin prepared by the present invention stores before solidifying and to solidify afterwards in for some time colour-change less, and its Gardner's colourity is all less than or equal to 3.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just in order to further illustrate the features and advantages of the present invention, instead of restriction to invention claim.
The preparation method who the invention discloses a kind of resol, comprises the following steps:
A) under the effect of basic catalyst, phenolic compound, aldehyde compound, reductive agent and boron-containing compound are carried out to the first reaction, obtain reaction mixture;
B) by above-mentioned steps A) reaction mixture and the nitrogenous compound that obtain carry out second and react, and obtains resol.
The present invention, under the effect of basic catalyst, carries out the first reaction by phenolic compound, aldehyde compound, reductive agent and boron-containing compound, obtains reaction mixture, then carries out second with nitrogenous compound and react, and obtains resol.The present invention is in phenol-formaldehyde reaction process; the boron-containing compound of specified proportion, reductibility compound and nitrogenous compound are joined in reaction process according to distinctive ratio and order; boron-containing compound, reductibility compound, the direct or indirect polycondensation of participation phenolic aldehyde the interaction of nitrogenous compound three difference; effectively protect phenolic hydroxyl group not oxidized one-tenth quinones in the synthetic and curing whole process of resol, and do not affected other performances of resol.Thereby, along with variation and the solidification process in storage time of resol, the colourity of resol prepared by the present invention changes less, effectively solve the impact of storage time on color of resin, extend the duration of service of resin, do not affect again the original performance of resin, improved the operability of resin simultaneously.Light heat-reactive phenolic resin prepared by the present invention can be applicable to that impregnated paper, veneer sheet, matrix material etc. require light-colored resin or to color of resin stability and the high association area of persistent request.Experimental result shows, light heat-reactive phenolic resin prepared by the present invention stores before solidifying and to solidify afterwards in for some time colour-change less, and its Gardner's colourity is all less than or equal to 3.
The all raw materials of the present invention, are not particularly limited its source, with what buy on method preparation well known to those skilled in the art or market.
First the present invention under the effect of basic catalyst, carries out the first reaction by phenolic compound, aldehyde compound, reductive agent and boron-containing compound, obtains reaction mixture.
Described phenolic compound is preferably one or more in phenol, cresols, dimethyl phenol, nonylphenol, dihydroxyphenyl propane, Resorcinol, propylphenol and ethylphenol, more preferably phenol, cresols, dimethyl phenol, nonylphenol, dihydroxyphenyl propane, Resorcinol, propylphenol or ethylphenol, most preferably is phenol, dihydroxyphenyl propane or cresols; Described aldehyde compound is formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or trioxymethylene, more preferably formaldehyde, acetaldehyde or paraformaldehyde; Described basic catalyst is preferably one or more in alkalimetal oxide, alkali metal hydroxide, aminated compounds, ammoniacal liquor and strong base-weak acid salt, more preferably alkalimetal oxide, alkali metal hydroxide, aminated compounds, ammoniacal liquor or strong base-weak acid salt, most preferably is sodium hydroxide, potassium hydroxide, calcium oxide, triethylamine, ammoniacal liquor or sodium carbonate; Described reductive agent is preferably one or more in ferrous sulfate, POTASSIUM BOROHYDRIDE, sodium borohydride, boron oxide, lithium aluminum hydride, S-WAT and tin protochloride, more preferably ferrous sulfate, POTASSIUM BOROHYDRIDE, sodium borohydride, boron oxide, lithium aluminum hydride, S-WAT or tin protochloride, most preferably is POTASSIUM BOROHYDRIDE, sodium borohydride, boron oxide, lithium aluminum hydride, S-WAT or tin protochloride; Described boron-containing compound is preferably sodium tetraborate, sodium metaborate, boric acid, high boron lime borate, lime borate, barium metaborate, calcium metaborate, one or more in colemanite and metaboric acid, more preferably sodium tetraborate, sodium metaborate, boric acid, high boron lime borate, lime borate, barium metaborate, calcium metaborate, colemanite or metaboric acid, most preferably be sodium tetraborate, sodium metaborate, boric acid, lime borate or calcium metaborate; The mol ratio of described phenolic compound and aldehyde compound is preferably 1:(0.1～3.5), more preferably 1:(0.5～3.0); Described basic catalyst and phenolic compound mass ratio are preferably (0.001～0.3): 1, and more preferably (0.01～0.05): 1; The temperature of described the first reaction is preferably 60～80 DEG C, more preferably 63～78 DEG C, most preferably is 68～73 DEG C.
The present invention is not particularly limited above-mentioned reaction process, with phenol-formaldehyde reaction process well known to those skilled in the art, the present invention is for improving reaction effect and optimizing reaction process, preferably undertaken by following concrete steps, first under the effect of basic catalyst, phenolic compound, aldehyde compound and reductive agent are carried out to pre-reaction, obtain pre-reaction mixture, then the pre-reaction mixture and the boron-containing compound that above-mentioned steps are obtained react, and obtain reaction mixture.
The temperature of described pre-reaction is preferably 60～70 DEG C, more preferably 63～68 DEG C; The reaction times of described pre-reaction is preferably 1～3 hour, more preferably 1.5～2.5 hours; The temperature of described reaction is preferably 70～80 DEG C, more preferably 73～78 DEG C; The time of described reaction is preferably 1～3 hour, more preferably 1.5～2.5 hours; The present invention is not particularly limited other conditions of described pre-reaction, with the reaction conditions of this type of reaction well known to those skilled in the art; The present invention is not particularly limited the conversion unit of described pre-reaction, with the conversion unit of this type of reaction well known to those skilled in the art; The present invention is not particularly limited other conditions of described reaction, with the reaction conditions of this type of reaction well known to those skilled in the art; The present invention is not particularly limited the conversion unit of described reaction, with the conversion unit of this type of reaction well known to those skilled in the art.
The present invention is obtaining after above-mentioned reaction mixture, carries out second react with nitrogenous compound, obtains resol; Described nitrogenous compound is preferably one or more in diethanolamine, urea, trimeric cyanamide, dimethylethanolamine, trolamine, hydrazine, quadrol, ammonium sulfate and ammonium chloride, more preferably diethanolamine, urea, trimeric cyanamide, dimethylethanolamine, trolamine, hydrazine, quadrol, ammonium sulfate or ammonium chloride, most preferably is trolamine, trimeric cyanamide, quadrol, diethanolamine, urea or dimethylethanolamine; The mass ratio of described boron-containing compound, reductive agent and nitrogenous compound is preferably 1:(0.1～0.8): (0.5～2.0), more preferably 1:(0.3～0.6): (1.0～1.5); The total mass of described boron-containing compound, reductive agent and nitrogenous compound and the mass ratio of phenolic compound are preferably (0.01～0.3): 1, and more preferably (0.05～0.1): 1; The temperature of described the second reaction is preferably 80～90 DEG C, more preferably 83～88 DEG C.
The present invention is not particularly limited other conditions of described the second reaction, with the reaction conditions of this type of reaction well known to those skilled in the art; The present invention is not particularly limited the conversion unit of described the second reaction, with the conversion unit of this type of reaction well known to those skilled in the art.
The present invention is for optimizing reaction process and strengthening experiment effect, and preferably, in the time that the viscosity number (25 DEG C) of the second reaction product of reacting is 500～1000cp/25 DEG C, stopped reaction also carries out aftertreatment, finally obtains resol; Described viscosity number is preferably 500～1000cp/25 DEG C, more preferably 600～800cp/25 DEG C.
The present invention is not particularly limited the step of aftertreatment, with the post-processing step of resol building-up reactions well known to those skilled in the art, the present invention preferably carries out according to following steps, first the reaction product of above-mentioned the second reaction is carried out to vacuum distilling, then add organic solvent, question response product is lowered the temperature after dissolving completely, finally obtains heat cured resol; Described organic solvent is preferably one or more in methyl alcohol, ethanol, acetone, butanone, ethylene glycol, glycerol, ether, ethyl acetate and methyl acetate, more preferably one or more in methyl alcohol, ethanol, acetone, butanone, ethylene glycol, glycerol, ether, ethyl acetate and methyl acetate, most preferably are one or both in methyl alcohol, ethanol; The mass ratio of described organic solvent and phenolic compound is preferably (0.5～0.8): 1, and more preferably (0.6～0.7): 1; The temperature of described cooling is preferably 25～45 DEG C, more preferably 30～40 DEG C.
The present invention is not particularly limited the pressure of described vacuum distilling, with the pressure of conventional vacuum distilling well known to those skilled in the art; The present invention is not particularly limited other conditions of described vacuum distilling, with the vacuum distilling condition of routine well known to those skilled in the art; The present invention is not particularly limited the equipment of described vacuum distilling, with the vacuum distillation plant of routine well known to those skilled in the art; The present invention was not particularly limited the time of described vacuum distilling, and the present invention is preferably that the water content when described reaction product is 1%～10% by the set of time of vacuum distilling, stops vacuum distilling, described water content more preferably 3%～7%.
The present invention is after above-mentioned reactions steps, prepare light resol, it is carried out to performance verification and colorimetric detection, and all detection methods of the present invention all detect according to desired method in the detection method of published routine in industry or national Specification.
The present invention makes the method for automobile filter paper of resin with reference to the preparation method of the disclosed resol for automotive industry filter paper of patent CN102391451B, thermosetting resin prepared by the present invention is made automobile filter paper and is carried out performance verification, experimental result shows, automobile filter paper prepared by heat-reactive phenolic resin provided by the invention, test according to national standard " mensuration of GB/T454-2002 paper bursting strength " with bursting strength instrument, bursting strength is 360kPa; Test according to the method for Static bending in national standard " mensuration of GB/T22364-2008 paper and cardboard bending break stiffness " with deflection instrument, bending break stiffness is 5.83mNm.
The light heat-reactive phenolic resin that the present invention obtains above-mentioned preparation method stores 0～5 month before solidifying, and its Gardner's colourity is 1～2; By after the above-mentioned storage phenolic resin curing of 0～5 month, surveying its Gardner's colourity is 2～3.
In order further to understand the present invention, below in conjunction with embodiment, a kind of resol provided by the invention is described, protection scope of the present invention is not limited by the following examples.
Comparative example 1
First the formalin, the 20kg sodium hydroxide that are 37% by 1000kg phenol, 2000kg mass concentration are put into reactor and mix, be heated to 60 DEG C, isothermal reaction 2 hours, then be warming up to 70 DEG C, continue isothermal reaction after 2 hours, obtain reaction mixture.
Then above-mentioned reaction mixture is warming up to 80 DEG C and proceeds reaction, in the time that the viscosity number of reaction product is 800cp/25 DEG C, stopped reaction, then carry out vacuum distilling, in the time that moisture content is 6% in the reaction product of above-mentioned steps, stops vacuum distilling and add 700kg methyl alcohol, after the product that above-mentioned steps is obtained dissolves completely, finally be cooled to 35 DEG C, obtain ordinary hot solidity phenol-formaldehyde A.
Embodiment 1
First the formalin, the 9kg sodium borohydride that are 37% by 1000kg phenol, 450kg mass concentration are put into reactor and mix, add again 30kg sodium hydroxide, be heated to 60 DEG C, isothermal reaction 2 hours, then after adding 18kg sodium tetraborate, be warming up to again 70 DEG C, continue isothermal reaction after 2 hours, obtain reaction mixture.
After more above-mentioned reaction mixture being mixed with 25kg quadrol, under the temperature condition of 80 DEG C, react, in the time that the viscosity number of reaction product is 600cp/25 DEG C, stopped reaction, then carries out vacuum distilling, in the time that in the reaction product of above-mentioned steps, moisture content is 3%, stop vacuum distilling and add 500kg methyl alcohol, after the product that above-mentioned steps is obtained dissolves completely, be finally cooled to 35 DEG C, obtain light heat-reactive phenolic resin 1#.
Embodiment 2
First the formalin, the 12kg lithium aluminum hydride that are 37% by 1000kg phenol, 800kg mass concentration are put into reactor and mix, add again 20kg potassium hydroxide, be heated to 66 DEG C, isothermal reaction 2 hours, then after adding 15kg boric acid, be warming up to again 75 DEG C, continue isothermal reaction after 2 hours, obtain reaction mixture.
After more above-mentioned reaction mixture being mixed with 25kg urea, under the temperature condition of 80 DEG C, react, in the time that the viscosity number of reaction product is 800cp/25 DEG C, stopped reaction, then carries out vacuum distilling, in the time that in the reaction product of above-mentioned steps, moisture content is 5%, stop vacuum distilling and add 600kg acetone, after the product that above-mentioned steps is obtained dissolves completely, be finally cooled to 35 DEG C, obtain light heat-reactive phenolic resin 2#.
Embodiment 3
First the formalin, the 10kg POTASSIUM BOROHYDRIDE that are 37% by 1000kg phenol, 1500kg mass concentration are put into reactor and mix, add again 15kg triethylamine, be heated to 70 DEG C, isothermal reaction 2 hours, then after adding 20kg sodium metaborate, be warming up to again 78 DEG C, continue isothermal reaction after 2 hours, obtain reaction mixture.
After more above-mentioned reaction mixture being mixed with 26kg trimeric cyanamide, under the temperature condition of 90 DEG C, react, in the time that the viscosity number of reaction product is 500cp/25 DEG C, stopped reaction, then carries out vacuum distilling, in the time that in the reaction product of above-mentioned steps, moisture content is 8%, stop vacuum distilling and add 600kg ethanol, after the product that above-mentioned steps is obtained dissolves completely, be finally cooled to 35 DEG C, obtain light heat-reactive phenolic resin 3#.
Embodiment 4
First the formalin, the 11kg boron oxide that are 37% by 1000kg phenol, 1700kg mass concentration are put into reactor and mix, add again 45kg ammoniacal liquor, be heated to 68 DEG C, isothermal reaction 2 hours, then after adding 25kg lime borate, be warming up to again 75 DEG C, continue isothermal reaction after 2 hours, obtain reaction mixture.
After more above-mentioned reaction mixture being mixed with 24kg dimethylethanolamine, under the temperature condition of 90 DEG C, react, in the time that the viscosity number of reaction product is 700cp/25 DEG C, stopped reaction, then carries out vacuum distilling, in the time that in the reaction product of above-mentioned steps, moisture content is 7%, stop vacuum distilling and add 500kg ethyl acetate, after the product that above-mentioned steps is obtained dissolves completely, be finally cooled to 35 DEG C, obtain light heat-reactive phenolic resin 4#.
Embodiment 5
First the formalin, the 11kg boron oxide that are 37% by 1000kg phenol, 1700kg mass concentration are put into reactor and mix, add again 45kg ammoniacal liquor, be heated to 68 DEG C, isothermal reaction 2 hours, then after adding 25kg lime borate, be warming up to again 75 DEG C, continue isothermal reaction after 2 hours, obtain reaction mixture.
After more above-mentioned reaction mixture being mixed with 24kg dimethylethanolamine, under the temperature condition of 90 DEG C, react, in the time that the viscosity number of reaction product is 700cp/25 DEG C, stopped reaction, then carries out vacuum distilling, in the time that in the reaction product of above-mentioned steps, moisture content is 7%, stop vacuum distilling and add 500kg ethyl acetate, after the product that above-mentioned steps is obtained dissolves completely, be finally cooled to 35 DEG C, obtain light heat-reactive phenolic resin 5#.
Embodiment 6
First the formalin, the 12kg tin protochloride that are 37% by 1000kg phenol, 2500kg mass concentration are put into reactor and mix, add again 30kg sodium carbonate, be heated to 60 DEG C, isothermal reaction 2 hours, then after adding 30kg calcium metaborate, be warming up to again 75 DEG C, continue isothermal reaction after 2 hours, obtain reaction mixture.
After more above-mentioned reaction mixture being mixed with 43kg trolamine, under the temperature condition of 90 DEG C, react, in the time that the viscosity number of reaction product is 1000cp/25 DEG C, stopped reaction, then carries out vacuum distilling, in the time that in the reaction product of above-mentioned steps, moisture content is 6%, stop vacuum distilling and add 600kg ethanol, after the product that above-mentioned steps is obtained dissolves completely, be finally cooled to 35 DEG C, obtain light heat-reactive phenolic resin 6#.
Embodiment 7
Performance verification
Ordinary hot solidity phenol-formaldehyde A prepared comparative example 1 and the prepared light heat-reactive phenolic resin 1#～6# of embodiment 1～6 are carried out to performance comparison test.
The method of making automobile filter paper with reference to the preparation method of the disclosed resol for automotive industry filter paper of patent CN102391451B of resin, thermosetting resin prepared by the present invention is made automobile filter paper and is carried out performance verification, and concrete steps are:
1, be the concentration of solid content 10% with methyl alcohol by resol dilution prepared above-described embodiment 1～6, with methyl alcohol, resol prepared comparative example being diluted is the concentration of solid content 10%;
2, body paper is immersed in respectively in resin diluent;
3, take out under room temperature and dry;
4, be positioned over 150 DEG C of curing ovens 10 minutes;
5, take out and be put in climatic chamber 3 hours (25 DEG C of temperature and humidity 50%).
6, obtain testing sample car filter paper A and automobile filter paper 1#～6#.
Bursting strength (kPa)
Above-mentioned 7 samples are carried out to parallel testing with bursting strength instrument 3 times according to national standard " mensuration of GB/T454-2002 paper bursting strength ", contrast and experiment, referring to table 1, table 1 is the bursting strength (kPa) of automobile filter paper A and automobile filter paper 1#～6#.
The bursting strength (kPa) of table 1 automobile filter paper A and automobile filter paper 1#～6#
Can find out by the data in table 1, the prepared automobile filter paper A of ordinary hot solidity phenol-formaldehyde A prepared by light heat-reactive phenolic resin 1#～6# prepared automobile filter paper 1#～6# of the embodiment of the present invention 1～6 preparation and comparative example is basically identical in bursting strength performance, and this shows that the prepared light heat-reactive phenolic resin of the present invention can be applied to original association area completely.
Bending break stiffness (mNm)
Above-mentioned 7 samples are carried out to parallel testing with deflection instrument 3 times according to the method for Static bending in national standard " mensuration of GB/T22364-2008 paper and cardboard bending break stiffness ", contrast and experiment, referring to table 2, table 2 is the bending break stiffness (mNm) of automobile filter paper A and automobile filter paper 1#～6#.
The bending break stiffness of table 2 automobile filter paper A and automobile filter paper 1#～6# (
mnm)
Can find out by the data in table 2, the prepared automobile filter paper A of ordinary hot solidity phenol-formaldehyde A prepared by light heat-reactive phenolic resin 1#～6# prepared automobile filter paper 1#～6# of the embodiment of the present invention 1～6 preparation and comparative example is basically identical in bursting strength performance, and this shows that the prepared light heat-reactive phenolic resin of the present invention can be applied to original association area completely.
Colourity checking
Ordinary hot solidity phenol-formaldehyde A prepared comparative example 1 and the prepared light heat-reactive phenolic resin 1#～6# of embodiment 1～6 are carried out to color contrast test.
Gardner's colourity before solidifying
By ordinary hot solidity phenol-formaldehyde A prepared comparative example 1 and the prepared light heat-reactive phenolic resin 1#～6# of embodiment 1～6, all at 0～10 DEG C, store respectively 1 month, 3 months, 5 months, and measure its Gardner's colourity, test result is referring to table 3, and table 3 is Gardner's colourity of phenol-formaldehyde A and different shelf liveves of resol 1#～6#.
Gardner's colourity of table 3 phenol-formaldehyde A and different shelf liveves of resol 1#～6#
Measuring result by Gardner's colourity in table 3 can be found out, the synthetic light heat-reactive phenolic resin 1#～6# of embodiment 1～6 with respect to the synthetic common heat-reactive phenolic resin of comparative example 1 before solidifying in different shelf lives colourity variation less, there is good colour stability, and can before solidifying, effectively keep look Gardner colourity to be less than or equal to 2.
Gardner's colourity after solidifying
By ordinary hot solidity phenol-formaldehyde A prepared comparative example 1 and the prepared light heat-reactive phenolic resin 1#～6# of embodiment 1～6, at 110 DEG C, solidify respectively after 30min, measure its solidify after Gardner's colourity, test result is referring to table 4, and table 4 is the Gardner's colourity after phenol-formaldehyde A and resol 1#～6# solidify.
Gardner's colourity after table 4 phenol-formaldehyde A and resol 1#～6# solidify
Measuring result by Gardner's colourity in table 4 can be found out, the colourity of the common heat-reactive phenolic resin that the synthetic light heat-reactive phenolic resin 1#～6# of embodiment 1～6 synthesizes with respect to comparative example 1 after solidifying changes less, there is good colour stability, and can after solidifying, effectively keep look Gardner colourity to be less than or equal to 3.
Can find out from above-mentioned correlation data, along with variation and the solidification process in storage time of resol, the colourity of resol prepared by the present invention changes less, effectively solve the impact of storage time on color of resin, extend the duration of service of resin, do not affect again the original performance of resin, improved the operability of resin simultaneously.Light heat-reactive phenolic resin prepared by the present invention can be applicable to that impregnated paper, veneer sheet, matrix material etc. require light-colored resin or to color of resin stability and the high association area of persistent request.
Above the preparation method of a kind of resol provided by the present invention is described in detail.Applied a concrete example herein principle of the present invention and embodiment are set forth, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. a preparation method for resol, comprises the following steps:
A) under the effect of basic catalyst, phenolic compound, aldehyde compound, reductive agent and boron-containing compound are carried out to the first reaction, obtain reaction mixture;
B) by above-mentioned steps A) reaction mixture and the nitrogenous compound that obtain carry out second and react, and obtains resol.
2. preparation method according to claim 1, is characterized in that, described basic catalyst is one or more in alkalimetal oxide, alkali metal hydroxide, aminated compounds, ammoniacal liquor and strong base-weak acid salt.
3. preparation method according to claim 1, is characterized in that, described reductive agent is one or more in ferrous sulfate, POTASSIUM BOROHYDRIDE, sodium borohydride, boron oxide, lithium aluminum hydride, S-WAT and tin protochloride.
4. preparation method according to claim 1, is characterized in that, described boron-containing compound is sodium tetraborate, sodium metaborate, boric acid, high boron lime borate, lime borate, barium metaborate, calcium metaborate, one or more in colemanite and metaboric acid.
5. preparation method according to claim 1, is characterized in that, described nitrogenous compound is one or more in diethanolamine, urea, trimeric cyanamide, dimethylethanolamine, trolamine, hydrazine, quadrol, ammonium sulfate and ammonium chloride.
6. preparation method according to claim 1, is characterized in that, described phenolic compound is one or more in phenol, cresols, dimethyl phenol, nonylphenol, dihydroxyphenyl propane, Resorcinol, propylphenol and ethylphenol; Described aldehyde compound is formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or trioxymethylene.
7. preparation method according to claim 1, is characterized in that, the mol ratio of described phenolic compound and aldehyde compound is 1:(0.1～3.5); Described basic catalyst and phenolic compound mass ratio are (0.001～0.3): 1.
8. preparation method according to claim 1, is characterized in that, the total mass of described boron-containing compound, reductive agent and nitrogenous compound and the mass ratio of phenolic compound are (0.01～0.3): 1; The mass ratio of described boron-containing compound, reductive agent and nitrogenous compound is 1:(0.1～0.8): (0.5～2.0).
9. preparation method according to claim 1, is characterized in that, the temperature of described the first reaction is 60～80 DEG C, and the temperature of described the second reaction is 80～90 DEG C.
10. preparation method according to claim 1, is characterized in that, described steps A) be specially:
A1) under the effect of basic catalyst, phenolic compound, aldehyde compound and reductive agent are carried out to pre-reaction, obtain pre-reaction mixture;
A2) pre-reaction mixture and the boron-containing compound that above-mentioned steps are obtained react, and obtain reaction mixture;
The temperature of described pre-reaction is 60～70 DEG C, and the temperature of described reaction is 70～80 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955117A (en) * | 2017-11-14 | 2018-04-24 | 太尔胶粘剂(广东)有限公司 | A kind of termite-proof, fire resisting phenolic resin preparation method |
| CN110588128A (en) * | 2019-10-12 | 2019-12-20 | 北京新福润达绝缘材料有限责任公司 | Preparation method of high-temperature-resistant and humidity-resistant electric halogen-free flame-retardant glass cloth laminated board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880434A (en) * | 2010-07-15 | 2010-11-10 | 山东圣泉化工股份有限公司 | Anhydrous type phenolic resin, preparation method thereof and application thereof |
| CN103435767A (en) * | 2013-09-06 | 2013-12-11 | 山东圣泉化工股份有限公司 | Phenolic resin emulsion and preparation method thereof |
-
2014
- 2014-02-28 CN CN201410072382.9A patent/CN103833946A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880434A (en) * | 2010-07-15 | 2010-11-10 | 山东圣泉化工股份有限公司 | Anhydrous type phenolic resin, preparation method thereof and application thereof |
| CN103435767A (en) * | 2013-09-06 | 2013-12-11 | 山东圣泉化工股份有限公司 | Phenolic resin emulsion and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955117A (en) * | 2017-11-14 | 2018-04-24 | 太尔胶粘剂(广东)有限公司 | A kind of termite-proof, fire resisting phenolic resin preparation method |
| CN110588128A (en) * | 2019-10-12 | 2019-12-20 | 北京新福润达绝缘材料有限责任公司 | Preparation method of high-temperature-resistant and humidity-resistant electric halogen-free flame-retardant glass cloth laminated board |
| CN110588128B (en) * | 2019-10-12 | 2021-10-15 | 北京新福润达绝缘材料有限责任公司 | Preparation method of high-temperature-resistant and humidity-resistant electric halogen-free flame-retardant glass cloth laminated board |
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