CN103613729A - Method for preparing modified phenolic resin - Google Patents
Method for preparing modified phenolic resin Download PDFInfo
- Publication number
- CN103613729A CN103613729A CN201310694180.3A CN201310694180A CN103613729A CN 103613729 A CN103613729 A CN 103613729A CN 201310694180 A CN201310694180 A CN 201310694180A CN 103613729 A CN103613729 A CN 103613729A
- Authority
- CN
- China
- Prior art keywords
- compound
- temperature
- reaction
- modified phenolic
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a method for preparing modified phenolic resin. The method comprises the following steps: heating phenolic compounds, aldehyde compounds and water to carry out a first reaction in the presence of a catalyst to obtain a reaction mixture; mixing the reaction mixture obtained in the abovementioned step with phenol and formaldehyde to carry out a second reaction in the presence of an alkaline catalyst to obtain the modified phenolic resin, wherein the catalyst is a bivalent metal salt or a divalent metal oxide. The method provided by the invention is used for preparing the modified phenolic resin with short curing time and low warpage in two steps of segmented reactions under special reaction conditions according to a special feeding sequence.
Description
Technical field
The invention belongs to technical field of polymer materials, relate in particular to a kind of preparation method of modified phenolic resins.
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.
Along with science and technology and economic fast development, in industry, the demand of moulding compound is increased day by day, simultaneously more and more stricter to the requirement of working accuracy, corresponding to the specification of quality of the resol as moulding compound material also corresponding raising, especially better geometrical dimension stability.
In existing production technique, common resol because set time is long, affects its production efficiency in moulding process, causes production cost to rise, and is difficult to meet the requirement of present stage large-scale commercial production.And the resol with fast setting characteristic in moulding process because curing speed is fast, can cause mobility only to keep very short time, under high pressure the short period of time is injected mould by material to needs, the moulded work of result in mould often produces unrelieved stress, and when after disengaging from mould, the unrelieved stress in process of cooling in moulded work, makes moulded work that warpage and distortion easily occur, cause moulded work qualification rate to decline, scrap rate rises.And when resin is under high pressure injected to mould, between mould, the normal space that forms, inevitably generates flash, finally forms waste material contaminate environment.
Therefore, how improving on the basis of phenolic resin curing time, reduce again the warpage degree in moulding process simultaneously, reduce flash, become problem demanding prompt solution in the industry.
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 modified phenolic resins, modified phenolic resins provided by the invention, when curing, has lower warpage and less flash, has set time faster with respect to common resol simultaneously.
The preparation method who the invention provides a kind of modified phenolic resins, comprises the following steps:
A) under the effect of catalyzer, phenolic compound, aldehyde compound and water heating are carried out to the first reaction, obtain reaction mixture;
B) under the effect of basic catalyst, by above-mentioned steps A) reaction mixture that obtains, phenol and formaldehyde mixes and carries out the second reaction, obtains modified phenolic resins;
Described catalyzer is divalent metal salt or bivalent metal oxide;
The total mass of described aldehyde compound and water and the mass ratio of phenolic compound are (0.2～1.2): 1;
The ratio of the quality of described aldehyde compound and described aldehyde compound and described water total mass is (0.3～0.4): 1.
Preferably, described phenolic compound is one or more in phenol, cresols, dimethyl phenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, propylphenol and ethylphenol.
Preferably, described aldehyde compound is formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or trioxymethylene.
Preferably, described basic catalyst is KOH, K
2cO
3, NaOH or Na
2cO
3.
Preferably, described catalyzer is zinc acetate, zinc oxide, manganese acetate, manganese oxide, cadmium acetate, Cadmium oxide, Cobaltous diacetate, cobalt oxide, neutralized verdigris or cupric oxide.
Preferably, the mass ratio of described catalyzer and phenolic compound is (0.01～0.03): 1.
Preferably, phenol and steps A described step B)) in the mass ratio of phenolic compound be 1:(0.1～0.5); Described step B) formaldehyde and steps A in) in the mass ratio of phenolic compound be 1:(0.07～0.35); Described step B) neutral and alkali catalyzer and step B) in the mass ratio of phenol be (0.01～0.05): 1.
Preferably, the temperature of described the second reaction is 40～80 ℃; The time of described the second reaction is 4～7 hours.
Preferably, described steps A) be specially:
Under the effect of catalyzer, phenolic compound, aldehyde compound and water are heated to the first temperature and react, reheat to the second temperature and react, be finally heated to the 3rd temperature and react, obtain reaction mixture;
Described the first temperature is 70～85 ℃, and the time of reacting at described the first temperature is 0.5～2 hour;
Described the second temperature is 86～95 ℃, and the time of reacting at described the second temperature is 0.5～2 hour;
Described the 3rd temperature is 96～110 ℃, and the time of reacting at described the 3rd temperature is 2～5 hours.
The preparation method who the invention provides a kind of modified phenolic resins, comprises the following steps: under the effect of catalyzer, phenolic compound, aldehyde compound and water heating are carried out to the first reaction, obtain reaction mixture; Again under the effect of basic catalyst, by above-mentioned steps A) reaction mixture that obtains, phenol and formaldehyde mixes and carries out the second reaction, obtains modified phenolic resins; Described catalyzer is divalent metal salt or bivalent metal oxide; The total mass of described aldehyde compound and water and the mass ratio of phenolic compound are (0.2～1.2): 1; The ratio of the quality of described aldehyde compound and described aldehyde compound and described water total mass is (0.3～0.4): 1.Compared with prior art, the present invention, by two step segmentation reactions and specific reaction conditions and order of addition(of ingredients), has obtained having the modified phenolic resins of very fast set time and lower warpage.The warpage of the modified phenolic resins that the present invention prepares in solidification process is 0.022mm, reduced approximately 50%, and in solidification process, have less flash with respect to the warpage of common resol.
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 are described is in order to further illustrate the features and advantages of the present invention, rather than the restriction to invention claim.
The preparation method who the invention discloses a kind of modified phenolic resins, comprises the following steps:
A) under the effect of catalyzer, phenolic compound, aldehyde compound and water heating are carried out to the first reaction, obtain reaction mixture;
B) under the effect of basic catalyst, by above-mentioned steps A) reaction mixture that obtains, phenol and formaldehyde mixes and carries out the second reaction, obtains modified phenolic resins;
Described catalyzer is divalent metal salt or bivalent metal oxide;
The total mass of described aldehyde compound and water and the mass ratio of phenolic compound are (0.2～1.2): 1;
The ratio of the quality of described aldehyde compound and described aldehyde compound and described water total mass is (0.3～0.4): 1.
First the present invention carries out the first reaction by phenolic compound, aldehyde compound and water heating under the effect of catalyzer, obtain reaction mixture, under the effect of basic catalyst, above-mentioned reaction mixture, phenol and formaldehyde are mixed and carries out the second reaction again, obtain modified phenolic resins.The present invention, by two step segmentation reactions and specific reaction conditions, has suppressed the generation of side reaction.The present invention, by two step segmentation reactions and specific reaction conditions and order of addition(of ingredients), has obtained having the modified phenolic resins of very fast set time and lower warpage.The warpage of the modified phenolic resins that the present invention prepares in solidification process is 0.022mm, reduced approximately 50%, and in solidification process, have less flash with respect to the warpage of common resol.
The all raw materials of the present invention, are not particularly limited its source, on market, buy.
First the present invention carries out the first reaction by phenolic compound, aldehyde compound and water heating under the effect of catalyzer, obtains reaction mixture.
Described catalyzer is preferably divalent metal salt or bivalent metal oxide, more preferably zinc acetate, zinc oxide, manganese acetate, manganese oxide, cadmium acetate, Cadmium oxide, Cobaltous diacetate, cobalt oxide, neutralized verdigris or cupric oxide, most preferably be zinc acetate, manganese oxide, Cadmium oxide or Cobaltous diacetate; Described phenolic compound is preferably phenol, cresols, dimethyl phenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, propylphenol or ethylphenol, more preferably cresols, nonylphenol, Bisphenol F or propylphenol; Described aldehyde compound is preferably formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or trioxymethylene, more preferably formaldehyde, butyraldehyde or paraformaldehyde; The total mass of described aldehyde compound and water and the mass ratio of phenolic compound are preferably (0.2～1.2): 1, more preferably (0.5～1.0): 1; The ratio of the quality of described aldehyde compound and described aldehyde compound and described water total mass is preferably (0.3～0.4): 1, more preferably (0.32～0.38): 1; The mass ratio of described catalyzer and phenolic compound is preferably (0.01～0.03): 1, more preferably (0.015～0.025): 1.
The present invention is not particularly limited above-mentioned reactions steps, for obtaining the modified phenolic resins that performance is more excellent, preferably carry out gradient-heated reaction, specifically according to following steps, carry out: under the effect of catalyzer, phenolic compound, aldehyde compound and water are heated to the first temperature to react, reheat to the second temperature and react, be finally heated to the 3rd temperature and react, obtain reaction mixture.
Described the first temperature is preferably 70～85 ℃, more preferably 73～82 ℃; The time of reacting at described the first temperature is preferably 0.5～2 hour, more preferably 0.8～1.7 hour; Described the second temperature is preferably 86～95 ℃, more preferably 88～93 ℃; The time of reacting at described the second temperature is preferably 0.5～2 hour, more preferably 0.8～1.7 hour; Described the 3rd temperature is preferably 96～110 ℃, more preferably 98～108 ℃; The time of reacting at described the 3rd temperature is preferably 2～5 hours, more preferably 3～4 hours.
The present invention is not particularly limited other conditions of reaction, with phenol-formaldehyde reaction condition well known to those skilled in the art; The present invention is not particularly limited order of addition(of ingredients), for reaction raw materials is mixed, preferably first aldehyde compound is first mixed with water, then mixes with phenolic compound; The present invention is not particularly limited the mode of heating, with type of heating well known to those skilled in the art; The present invention is more steady for guaranteeing reaction, preferably in reaction process, stirs; The present invention is not particularly limited the condition stirring, with alr mode well known to those skilled in the art.
The present invention is then under the effect of basic catalyst, and the second reaction is carried out in the reaction mixture that above-mentioned steps is obtained, phenol and formaldehyde mixing, obtains modified phenolic resins.
Described step B) phenol and steps A in) in the mass ratio of phenolic compound be preferably 1:(0.1～0.5), 1:(0.2～0.4 more preferably); Described step B) formaldehyde and steps A in) in the mass ratio of phenolic compound be preferably 1:(0.07-0.35), 1:(0.10～0.32 more preferably); Described step B) neutral and alkali catalyzer and step B) in the mass ratio of phenol be preferably (0.01～0.05): 1, more preferably (0.02～0.04): 1; The temperature of described the second reaction is preferably 40～80 ℃, more preferably 50～70 ℃; The time of described the second reaction is preferably 4～7 hours, more preferably 5～6 hours.
The present invention has prepared modified phenolic resins by aforesaid method, and the number-average molecular weight of described modified phenolic resins is preferably 200～2000, and more preferably 400～1800; The viscosity of described modified phenolic resins at 50 ℃ is preferably 500m～15000mPa.s; The polymerization degree of described modified phenolic resins is preferably 2～10, and more preferably 3～9.
The present invention is not particularly limited other conditions of reaction, with phenol-formaldehyde reaction well known to those skilled in the art; The present invention is not particularly limited the mode of heating, with type of heating well known to those skilled in the art; The present invention is more steady for guaranteeing reaction, preferably in reaction process, stirs; The present invention is not particularly limited the condition stirring, with alr mode well known to those skilled in the art.
The present invention is after obtaining above-mentioned modified phenolic resins, and the ratio that is 1:2:0.01 according to mass ratio by modified phenolic resins, epoxy resin (E51 type) and imidazoles is carried out batch mixing, obtains compound; Then above-mentioned compound is put into mould, with carrying out hot pressing in hot-press equipment.
The present invention is not particularly limited described mould, with common die well known to those skilled in the art, is preferably long 20cm, wide 10cm, the common die of thick 3mm; The present invention is not particularly limited hot-press equipment, with hot-press equipment well known to those skilled in the art, is preferably SM100T press (device name); The present invention is not particularly limited the temperature and pressure of hot pressing, the temperature and pressure with resol hot pressing well known to those skilled in the art during for mold materials.
Technological process to above-mentioned hot pressing detects by national standard, result shows, the warpage of the compound that contains the modified phenolic resins that the present invention prepares in solidification process is 0.022mm, degree of mobilization is 85cm, gel time is 80 seconds, warpage with respect to common resol has reduced approximately 50%, and degree of mobilization and gel time are moderate, and in solidification process, has less flash.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of modified phenolic resins provided by the invention is described, protection scope of the present invention is not limited by the following examples.
Comparative example 1
First by 10g phenol, 7g mass concentration is the reactor that 37% formaldehyde solution and 0.1g zinc powder are put into 1L, open to stir and be heated to 80 ℃ and react, react after 1 hour, be warmed up to 90 ℃ and continue reaction, react after 1 hour, be warmed up to 100 ℃ and continue reaction, react after 3 hours, obtain resol, molecular weight Mn is 510.
The ratio that is 1:2:0.01 according to mass ratio by above-mentioned resol, epoxy resin (E51 type) and imidazoles is carried out batch mixing, obtains compound.Then above-mentioned compound is put into long 20cm, wide 10cm, in thick 3mm grinding tool, carries out hot pressing with SM100T press.
The technological process of above-mentioned hot pressing is detected with resol > > according to national standard < < GB/T24411-2009 friction materials, result shows, the compound gel time in solidification process that contains modified phenolic resins prepared by the present embodiment is 60 seconds, and degree of mobilization is 64cm.
The technological process of above-mentioned hot pressing is tested according to the method for stipulating in IPC-4101 testing method handbook, and result shows, the compound warpage in solidification process that contains modified phenolic resins prepared by the present embodiment is 0.04mm.
Technological process to above-mentioned hot pressing detects, and result shows, the compound flash in solidification process that contains resol prepared by this comparative example is more.
Comparative example 2
First by 10g phenol, 7g mass concentration is the reactor that 37% formaldehyde solution and 0.1g oxalic acid are put into 1L, open to stir and be heated to 80 ℃ and react, react after 1 hour, be warmed up to 90 ℃ and continue reaction, react after 1 hour, be warmed up to 100 ℃ and continue reaction, react after 3 hours, obtain resol, molecular weight Mn is 520.
The ratio that is 1:2:0.01 according to mass ratio by above-mentioned resol, epoxy resin (E51 type) and imidazoles is carried out batch mixing, obtains compound.Then above-mentioned compound is put into long 20cm, wide 10cm, in thick 3mm grinding tool, carries out hot pressing with SM100T press.
The technological process of above-mentioned hot pressing is detected with resol > > according to national standard < < GB/T24411-2009 friction materials, result shows, the compound gel time in solidification process that contains modified phenolic resins prepared by the present embodiment is 130 seconds, and degree of mobilization is 120cm.
The technological process of above-mentioned hot pressing is tested according to the method for stipulating in IPC-4101 testing method handbook, and result shows, the compound warpage in solidification process that contains modified phenolic resins prepared by the present embodiment is 0.042mm.
Technological process to above-mentioned hot pressing detects, and result shows, the compound flash in solidification process that contains resol prepared by this comparative example is more.
Comparative example 3
First by 10g bis-phenol a, 7g mass concentration is the reactor that 37% formaldehyde solution and 0.1g oxalic acid are put into 1L, open to stir and be heated to 80 ℃ and react, react after 1 hour, be warmed up to 90 ℃ and continue reaction, react after 1 hour, be warmed up to 100 ℃ and continue reaction, react after 3 hours, obtain resol, molecular weight Mn is 510.
The ratio that is 1:2:0.01 according to mass ratio by above-mentioned resol, epoxy E51 resin and imidazoles is carried out batch mixing, obtains compound.Then above-mentioned compound is put into long 20cm, wide 10cm, in thick 3mm grinding tool, carries out hot pressing with SM100T press.
The technological process of above-mentioned hot pressing is detected with resol > > according to national standard < < GB/T24411-2009 friction materials, result shows, the compound gel time in solidification process that contains modified phenolic resins prepared by the present embodiment is 120 seconds, and degree of mobilization is 110cm.
The technological process of above-mentioned hot pressing is tested according to the method for stipulating in IPC-4101 testing method handbook, and result shows, the compound warpage in solidification process that contains modified phenolic resins prepared by the present embodiment is 0.042mm.
Technological process to above-mentioned hot pressing detects, and result shows, compound flash in solidification process of the resol that contains the preparation of this comparative example example is more.
Comparative example 4
100g phenol, 70g formaldehyde and 1g oxalic acid are joined there is thermometer, in the 100ml reactor of whipping appts and reflux exchanger, wherein formaldehyde is that mass concentration is 37% formalin, be heated to 80 ℃, isothermal reaction 1h, be warmed up to 90 ℃, isothermal reaction 1h, continues to be warmed up to 100 ℃, isothermal reaction 3h, obtains reaction mixture.
In above-mentioned reaction mixture, put into 10g phenol again, the formaldehyde solution that 7g mass concentration is 37% and 0.1g zinc powder are put into the reactor of 1L, open to stir and be heated to 90 ℃ and react, and react after 5 hours, obtain resol, and molecular weight Mn is 480.
The ratio that is 1:2:0.01 according to mass ratio by above-mentioned resol, epoxy resin (E51 type) and imidazoles is carried out batch mixing, obtains compound.Then above-mentioned compound is put into long 20cm, wide 10cm, in thick 3mm grinding tool, carries out hot pressing with SM100T press.
The technological process of above-mentioned hot pressing is detected with resol > > according to national standard < < GB/T24411-2009 friction materials, result shows, the compound gel time in solidification process that contains modified phenolic resins prepared by the present embodiment is 110 seconds, and degree of mobilization is 110cm.
The technological process of above-mentioned hot pressing is tested according to the method for stipulating in IPC-4101 testing method handbook, and result shows, the compound warpage in solidification process that contains modified phenolic resins prepared by the present embodiment is 0.041mm.
Technological process to above-mentioned hot pressing detects, and result shows, the compound flash in solidification process that contains resol prepared by this comparative example is more.
Embodiment 1
First by 10g phenol, 7g mass concentration is the reactor that 37% formaldehyde solution and 0.1g zinc powder are put into 1L, open to stir and be heated to 80 ℃ and react, react after 1 hour, be warmed up to 90 ℃ and continue reaction, react after 1 hour, be warmed up to 100 ℃ and continue reaction, react after 3 hours, obtain reaction mixture.
Then the formaldehyde solution that is 37% by 100g phenol, 120g mass concentration and 1g sodium hydroxide add in above-mentioned reactor, be stirred to fully and mix with above-mentioned reaction mixture, be finally heated to 50 ℃ and react, react after 4 hours, obtain modified phenolic resins, molecular weight Mn is 500.
The ratio that is 1:2:0.01 according to mass ratio by above-mentioned modified phenolic resins, epoxy resin and imidazoles is carried out batch mixing, obtains compound.Then above-mentioned compound is put into long 20cm, wide 10cm, in thick 3mm grinding tool, carries out hot pressing with 100T press.
The technological process of above-mentioned hot pressing is detected with resol > > according to national standard < < GB/T 24411-2009 friction materials, result shows, the compound gel time in solidification process that contains modified phenolic resins prepared by the present embodiment is 100 seconds, and degree of mobilization is 104cm.
The technological process of above-mentioned hot pressing is tested according to the method for stipulating in IPC-4101 testing method handbook, and result shows, the compound warpage in solidification process that contains modified phenolic resins prepared by the present embodiment is 0.021mm.
Technological process to above-mentioned hot pressing detects, and result shows, the compound that contains modified phenolic resins prepared by the present embodiment has less flash in solidification process.
Embodiment 2
First by 10g phenol, 8g mass concentration is the reactor that 37% formaldehyde solution and 0.1g zinc powder are put into 1L, open to stir and be heated to 80 ℃ and react, react after 1 hour, be warmed up to 90 ℃ and continue reaction, react after 1 hour, be warmed up to 100 ℃ and continue reaction, react after 3 hours, obtain reaction mixture.
Then the formaldehyde solution that is 37% by 100g phenol, 140g mass concentration and 1g sodium hydroxide add in above-mentioned reactor, be stirred to fully and mix with above-mentioned reaction mixture, be finally heated to 50 ℃ and react, react after 4 hours, obtain modified phenolic resins, molecular weight Mn is 480.
The ratio that is 1:2:0.01 according to mass ratio by above-mentioned modified phenolic resins, epoxy resin (E51 type) and imidazoles is carried out batch mixing, obtains compound.Then above-mentioned compound is put into long 20cm, wide 10cm, in thick 3mm grinding tool, carries out hot pressing with SM100T press.
The technological process of above-mentioned hot pressing is detected with resol > > according to national standard < < GB/T 24411-2009 friction materials, result shows, the compound gel time in solidification process that contains modified phenolic resins prepared by the present embodiment is 100 seconds, and degree of mobilization is 104cm.
The technological process of above-mentioned hot pressing is tested according to the method for stipulating in IPC-4101 testing method handbook, and result shows, the compound warpage in solidification process that contains modified phenolic resins prepared by the present embodiment is 0.022mm.
Technological process to above-mentioned hot pressing detects, and result shows, the compound that contains modified phenolic resins prepared by the present embodiment has less flash in solidification process.
Embodiment 3
First by 10g bis-phenol a, 8g mass concentration is the reactor that 37% formaldehyde solution and 0.1g zinc powder are put into 1L, open to stir and be heated to 80 ℃ and react, react after 1 hour, be warmed up to 90 ℃ and continue reaction, react after 1 hour, be warmed up to 100 ℃ and continue reaction, react after 3 hours, obtain reaction mixture.
Then the formaldehyde solution that is 37% by 100g bis-phenol a, 140g mass concentration and 1g sodium hydroxide add in above-mentioned reactor, be stirred to fully and mix with above-mentioned reaction mixture, be finally heated to 50 ℃ and react, react after 4 hours, obtain modified phenolic resins, molecular weight Mn is 520.
The ratio that is 1:2:0.01 according to mass ratio by above-mentioned modified phenolic resins, epoxy resin (E51 type) and imidazoles is carried out batch mixing, obtains compound.Then above-mentioned compound is put into long 20cm, wide 10cm, in thick 3mm grinding tool, carries out hot pressing with SM100T press.
The technological process of above-mentioned hot pressing is detected with resol > > according to national standard < < GB/T 24411-2009 friction materials, result shows, the compound gel time in solidification process that contains modified phenolic resins prepared by the present embodiment is 100 seconds, and degree of mobilization is 104cm.
The technological process of above-mentioned hot pressing is tested according to the method for stipulating in IPC-4101 testing method handbook, and result shows, the compound warpage in solidification process that contains modified phenolic resins prepared by the present embodiment is 0.022mm.
Technological process to above-mentioned hot pressing detects, and result shows, the compound that contains modified phenolic resins prepared by the present embodiment has less flash in solidification process.
Embodiment 4
First by 10g bis-phenol a, 7g mass concentration is the reactor that 37% formaldehyde solution and 0.1g zinc powder are put into 1L, open to stir and be heated to 80 ℃ and react, react after 1 hour, be warmed up to 90 ℃ and continue reaction, react after 1 hour, be warmed up to 100 ℃ and continue reaction, react after 3 hours, obtain reaction mixture.
Then the formaldehyde solution that is 37% by 100g bis-phenol a, 120g mass concentration and 1g sodium hydroxide add in above-mentioned reactor, be stirred to fully and mix with above-mentioned reaction mixture, be finally heated to 50 ℃ and react, react after 4 hours, obtain modified phenolic resins, molecular weight Mn is 530.
The ratio that is 1:2:0.01 according to mass ratio by above-mentioned modified phenolic resins, epoxy resin (E51 type) and imidazoles is carried out batch mixing, obtains compound.Then above-mentioned compound is put into long 20cm, wide 10cm, in thick 3mm grinding tool, carries out hot pressing with SM100T press.
The technological process of above-mentioned hot pressing is detected with resol > > according to national standard < < GB/T 24411-2009 friction materials, result shows, the compound gel time in solidification process that contains modified phenolic resins prepared by the present embodiment is 100 seconds, and degree of mobilization is 104cm.
The technological process of above-mentioned hot pressing is tested according to the method for stipulating in IPC-4101 testing method handbook, and result shows, the compound warpage in solidification process that contains modified phenolic resins prepared by the present embodiment is 0.021mm.
Technological process to above-mentioned hot pressing detects, and result shows, the compound that contains modified phenolic resins prepared by the present embodiment has less flash in solidification process.
Above the preparation method of a kind of modified phenolic resins 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 (9)
1. a preparation method for modified phenolic resins, comprises the following steps:
A) under the effect of catalyzer, phenolic compound, aldehyde compound and water heating are carried out to the first reaction, obtain reaction mixture;
B) under the effect of basic catalyst, by above-mentioned steps A) reaction mixture that obtains, phenol and formaldehyde mixes and carries out the second reaction, obtains modified phenolic resins;
Described catalyzer is divalent metal salt or bivalent metal oxide;
The total mass of described aldehyde compound and water and the mass ratio of phenolic compound are (0.2～1.2): 1;
The ratio of the quality of described aldehyde compound and described aldehyde compound and described water total mass is (0.3～0.4): 1.
2. 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, Bisphenol F, Resorcinol, propylphenol and ethylphenol.
3. preparation method according to claim 1, is characterized in that, described aldehyde compound is formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde or trioxymethylene.
4. preparation method according to claim 1, is characterized in that, described basic catalyst is KOH, K
2cO
3, NaOH or Na
2cO
3.
5. preparation method according to claim 1, is characterized in that, described catalyzer is zinc acetate, zinc oxide, manganese acetate, manganese oxide, cadmium acetate, Cadmium oxide, Cobaltous diacetate, cobalt oxide, neutralized verdigris or cupric oxide.
6. preparation method according to claim 1, is characterized in that, the mass ratio of described catalyzer and phenolic compound is (0.01～0.03): 1.
7. preparation method according to claim 1, is characterized in that, described step B) in phenol and steps A) in the mass ratio of phenolic compound be 1:(0.1～0.5); Described step B) formaldehyde and steps A in) in the mass ratio of phenolic compound be 1:(0.07～0.35); Described step B) neutral and alkali catalyzer and step B) in the mass ratio of phenol be (0.01～0.05): 1.
8. preparation method according to claim 1, is characterized in that, the temperature of described the second reaction is 40～80 ℃; The time of described the second reaction is 4～7 hours.
9. preparation method according to claim 1, is characterized in that, described steps A) be specially:
Under the effect of catalyzer, phenolic compound, aldehyde compound and water are heated to the first temperature and react, reheat to the second temperature and react, be finally heated to the 3rd temperature and react, obtain reaction mixture;
Described the first temperature is 70～85 ℃, and the time of reacting at described the first temperature is 0.5～2 hour;
Described the second temperature is 86～95 ℃, and the time of reacting at described the second temperature is 0.5～2 hour;
Described the 3rd temperature is 96～110 ℃, and the time of reacting at described the 3rd temperature is 2～5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694180.3A CN103613729B (en) | 2013-12-16 | 2013-12-16 | A kind of preparation method of modified phenolic resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694180.3A CN103613729B (en) | 2013-12-16 | 2013-12-16 | A kind of preparation method of modified phenolic resins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103613729A true CN103613729A (en) | 2014-03-05 |
| CN103613729B CN103613729B (en) | 2015-11-25 |
Family
ID=50164456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310694180.3A Active CN103613729B (en) | 2013-12-16 | 2013-12-16 | A kind of preparation method of modified phenolic resins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103613729B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108609606A (en) * | 2018-06-25 | 2018-10-02 | 中国人民解放军国防科技大学 | Preparation method of carbon aerogel heat insulation material |
| CN111410936A (en) * | 2020-04-10 | 2020-07-14 | 荆门市诺维英新材料科技有限公司 | Composite fiber high-performance friction material and preparation method thereof |
| CN113801280A (en) * | 2021-11-16 | 2021-12-17 | 北京玻钢院复合材料有限公司 | Alkylphenol modified phenolic resin suitable for hot-melt presoaking process and preparation method thereof |
| CN114805716A (en) * | 2022-04-28 | 2022-07-29 | 蔚林新材料科技股份有限公司 | Modified phenolic resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177471A (en) * | 2007-12-12 | 2008-05-14 | 谢建军 | Method for producing phenol resin |
| CN101880367A (en) * | 2010-08-03 | 2010-11-10 | 山东圣泉化工股份有限公司 | Method for preparing high-ortho thermoplastic phenolic resin |
| CN102245664A (en) * | 2008-12-12 | 2011-11-16 | 旭有机材工业株式会社 | Phenol resin for shell molding, process for production of the resin, resin-coated sand for shell molding, and molds obtained using same |
-
2013
- 2013-12-16 CN CN201310694180.3A patent/CN103613729B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177471A (en) * | 2007-12-12 | 2008-05-14 | 谢建军 | Method for producing phenol resin |
| CN102245664A (en) * | 2008-12-12 | 2011-11-16 | 旭有机材工业株式会社 | Phenol resin for shell molding, process for production of the resin, resin-coated sand for shell molding, and molds obtained using same |
| CN101880367A (en) * | 2010-08-03 | 2010-11-10 | 山东圣泉化工股份有限公司 | Method for preparing high-ortho thermoplastic phenolic resin |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108609606A (en) * | 2018-06-25 | 2018-10-02 | 中国人民解放军国防科技大学 | Preparation method of carbon aerogel heat insulation material |
| CN108609606B (en) * | 2018-06-25 | 2020-03-06 | 中国人民解放军国防科技大学 | Preparation method of carbon aerogel heat insulation material |
| CN111410936A (en) * | 2020-04-10 | 2020-07-14 | 荆门市诺维英新材料科技有限公司 | Composite fiber high-performance friction material and preparation method thereof |
| CN113801280A (en) * | 2021-11-16 | 2021-12-17 | 北京玻钢院复合材料有限公司 | Alkylphenol modified phenolic resin suitable for hot-melt presoaking process and preparation method thereof |
| CN113801280B (en) * | 2021-11-16 | 2022-02-08 | 北京玻钢院复合材料有限公司 | Alkylphenol modified phenolic resin suitable for hot-melt presoaking process and preparation method thereof |
| CN114805716A (en) * | 2022-04-28 | 2022-07-29 | 蔚林新材料科技股份有限公司 | Modified phenolic resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103613729B (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103613729B (en) | A kind of preparation method of modified phenolic resins | |
| CN101845198B (en) | Method for preparing thermosetting phenolic resin film | |
| CN106317354B (en) | Thermostable phenolic resin and preparation method thereof | |
| CN102276775A (en) | Modified phenolic resin and phenolic resin composition | |
| CN101597364B (en) | Synthesis method of thermosetting phenol-formaldehyde resin in solid at normal temperature | |
| CN106632997B (en) | A kind of phosphorus-containing phenolic aldehyde epoxy hardener and preparation method thereof | |
| CN103254381A (en) | Preparation method of nitrogenous phenolic resin in one-step synthesis process | |
| CN104327229B (en) | Toughening modifying resol and preparation method thereof | |
| CN102153731A (en) | Room temperature curing heat-resistant epoxy curing agent | |
| CN103588942B (en) | High Performance Phenolic Resins composition and method of making the same | |
| KR20070085539A (en) | Hydroxy-aromatic compound, process for the preparation thereof, and use of the compound | |
| CN101454366A (en) | Process for the preparation of a hydroxy-aromatic resin: hydroxy-aromatic resin, and modification thereof | |
| CN106133017A (en) | Phenolic resin, comprise the composition epoxy resin of this phenolic resin, the solidfied material of this composition epoxy resin and there is the semiconductor device of this solidfied material | |
| CN104877096A (en) | Preparation method of modified phenol formaldehyde resin | |
| CN109535359A (en) | A method of alkali resistance phenolic resin is synthesized based on control solution ph | |
| CN103483765B (en) | A kind of phenol resin composition and preparation method thereof | |
| KR101610236B1 (en) | Phenol resin molding material | |
| CN102373621B (en) | Resin varnish composition with high temperature of glass transition for glass fiber laminated plate use | |
| CA1164141A (en) | Liquid novolak resin and products made therefrom | |
| CN102070757A (en) | Preparation method of water-dispersed phenolic resin | |
| JP4661087B2 (en) | Method for producing solid resol type phenolic resin | |
| CN103450263A (en) | Preparation method of phosphorus-modified phenolic resin | |
| CN104086728A (en) | Preparation method of modified phenolic resin | |
| CN103450422A (en) | Preparation method of phosphorus-modified phenolic resin | |
| CN103450421A (en) | Preparation method of phosphorus-modified phenolic resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of modified phenolic resin Effective date of registration: 20210506 Granted publication date: 20151125 Pledgee: Qilu bank Limited by Share Ltd. Ji'nan Zhangqiu branch Pledgor: JINAN SHENGQUAN HAWORTH RESIN Co.,Ltd. Registration number: Y2021980003262 |