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 dihydroxyphenyl propane formaldehyde epoxy resin, comprises the following steps:
A) under the condition of anaerobic, dihydroxyphenyl propane formaldehyde resin, epoxy chloropropane, reductive agent and phase-transfer catalyst heating are carried out to the first reaction, obtain the first reaction mixture;
B) under the effect of basic catalyst, by above-mentioned steps A) the first reaction mixture of obtaining carries out the second reaction, obtains dihydroxyphenyl propane formaldehyde epoxy resin.
The present invention is under the condition of anaerobic, dihydroxyphenyl propane formaldehyde resin, epoxy chloropropane, reductive agent and phase-transfer catalyst heating are reacted, obtain the first reaction mixture, then under the effect of basic catalyst, there is the second reaction in above-mentioned the first reaction mixture, obtains dihydroxyphenyl propane formaldehyde epoxy resin.The present invention, by two step segmentation reactions and specific reaction conditions, has suppressed the generation of side reaction.The dihydroxyphenyl propane formaldehyde epoxy resin that the present invention obtains has lower epoxy equivalent (weight), and hydrolyzable chlorine content is below 75ppm, and meanwhile, dihydroxyphenyl propane formaldehyde epoxy resin color prepared by the present invention is more shallow, colourimetric number is 1, has expanded the range of application of dihydroxyphenyl propane formaldehyde epoxy resin.
The all raw materials of the present invention, are not particularly limited its source, on market, buy.
First the present invention under the condition of anaerobic, carries out the first reaction by dihydroxyphenyl propane formaldehyde resin, epoxy chloropropane, reductive agent and phase-transfer catalyst heating, obtains the first reaction mixture, i.e. addition open loop obtains the intermediate of chloropharin ether structure.
The present invention is not particularly limited the source of dihydroxyphenyl propane formaldehyde resin, with preparation method well known to those skilled in the art, obtain or commercially available, dihydroxyphenyl propane formaldehyde resin of the present invention is preferably commercially available SH-2130 type dihydroxyphenyl propane formaldehyde resin (Shandong Shengquan Chemical Industry Co., Ltd.).
Described reductive agent is preferably Al, Zn, Fe, Na
2sO
3, FeSO
4in one or more, more preferably Al, Zn, Fe, Na
2sO
3or FeSO
4, most preferably be Zn, Fe or Na
2sO
3, described phase-transfer catalyst is preferably etamon chloride, Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, trityl group bromo-phosphonium, triphenyl ethyl bromo-phosphonium, BPP, benzyl tri-phenyl-phosphorus bromide, one or more in cetyl trimethylammonium bromide, etamon chloride more preferably, Tetrabutyl amonium bromide, benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, trityl group bromo-phosphonium, triphenyl ethyl bromo-phosphonium, BPP, benzyl tri-phenyl-phosphorus bromide or cetyl trimethylammonium bromide, most preferably be benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride or trityl group bromo-phosphonium, the mass ratio of described reductive agent and dihydroxyphenyl propane formaldehyde resin is preferably (0.001~0.02): 1, more preferably (0.005~0.015): 1, the mass ratio of described phase-transfer catalyst and dihydroxyphenyl propane formaldehyde resin is preferably (0.005~0.05): 1, more preferably (0.01~0.04): 1, the mass ratio of described epoxy chloropropane and dihydroxyphenyl propane formaldehyde resin is preferably (3~12): 1, more preferably (5~10): 1.The time of described the first reaction is preferably 4~8 hours, more preferably 5~7 hours; The temperature of described the first reaction is preferably 60~80 ℃, more preferably 65~75 ℃; The present invention is not particularly limited the form of reductive agent, for guaranteeing that reductive agent fully participates in reaction, is preferably powdery; The present invention is not particularly limited the order number of described powdery reductive agent, with the order number of powdery reductive agent well known to those skilled in the art.
The present invention is not particularly limited described oxygen free condition, and with eliminating oxygen method well known to those skilled in the art, in the present invention, concrete grammar preferably carries out according to following steps:
First reaction vessel is vacuumized, then carry out gas displacement to passing into high pure protective gas in reaction vessel, repeatable operation is further to get rid of remaining oxygen.The vacuum tightness of described vacuum is preferably 0.01~0.1MPa, more preferably 0.02~0.08MPa; Described high pure protective gas is preferably rare gas element or nitrogen, more preferably nitrogen; The purity of described high pure protective gas is preferably more than and equals 99.999%, is more preferably more than or equal to 99.9996%.The present invention is not particularly limited the number of times of described repeatable operation, is preferably 2~4 times; The present invention is not particularly limited the described equipment vacuumizing, with the equipment vacuumizing well known to those skilled in the art; The present invention passes into after high pure protective gas described, and reaction vessel internal pressure is not particularly limited, and with reaction pressure well known to those skilled in the art, is preferably normal pressure in the present invention; The present invention is not particularly limited reaction vessel, with well known to those skilled in the art for the synthetic container of dihydroxyphenyl propane formaldehyde epoxy resin; The present invention is not particularly limited the source of high pure protective gas, with preparation method well known to those skilled in the art, obtains or commercially available.
The present invention is not particularly limited the mode of described heating, with type of heating well known to those skilled in the art; The present invention is not particularly limited other conditions of reaction, for guaranteeing that reaction process is steady, preferably in reaction process, stirs; The present invention is not particularly limited the mode stirring, with alr mode well known to those skilled in the art.
The present invention is under the effect of the second basic catalyst, and the second reaction occurs the first reaction mixture that above-mentioned steps obtains, i.e. catalysis ring-closure reaction, obtains dihydroxyphenyl propane formaldehyde epoxy resin, and its process is specially:
To above-mentioned steps A) drip basic catalyst in the first reaction mixture of obtaining and carry out the second reaction, obtain dihydroxyphenyl propane formaldehyde epoxy resin.
Described basic catalyst is preferably KOH solution, K
2cO
3solution, NaOH solution, Na
2cO
3one or more in solution, more preferably KOH solution, K
2cO
3solution, NaOH solution or Na
2cO
3solution, most preferably is KOH solution or NaOH solution; The mass concentration of described basic catalyst is preferably 30~50%, and more preferably 45~50%; In described basic catalyst, the mass ratio of solute and dihydroxyphenyl propane formaldehyde resin is preferably (0.23~0.5): 1, more preferably (0.26~0.4): 1.
The time of described the second reaction is preferably 3~6 hours, more preferably 3.5~4.5 hours; The temperature of described the second reaction is preferably 60~90 ℃, more preferably 62~85 ℃; The pressure of described the second reaction, vacuum tightness, is preferably 0.01~0.1MPa, more preferably 0.015~0.04MPa; The time of described dropping is preferably 3~6 hours, more preferably 3.5~4.5 hours; The present invention is not particularly limited the speed of described dropping, is as the criterion with the reaction times, is preferably within the reaction times basic catalyst is dropwised.
The present invention is for guaranteeing steadily carrying out of reaction, prevent the generation of side reaction, preferably above-mentioned, add in the process that basic catalyst carries out the second reaction, remove the water in reaction system simultaneously, and finally at basic catalyst, add complete,, after having reacted, heat up and remove excessive epoxy chloropropane.The temperature of described intensification is preferably 130~160 ℃, more preferably 135~155 ℃; The present invention removes the method for water in reaction system and is not particularly limited described, to remove the method for water in dihydroxyphenyl propane formaldehyde epoxy resin building-up process well known to those skilled in the art; The present invention's other conditions when removing excessive epoxy chloropropane are not particularly limited, to remove the condition of excessive epoxy chloropropane in dihydroxyphenyl propane formaldehyde epoxy resin building-up process well known to those skilled in the art; The present invention is not particularly limited removing the method for excessive epoxy chloropropane, to remove the method for excessive epoxy chloropropane in dihydroxyphenyl propane formaldehyde epoxy resin building-up process well known to those skilled in the art.
The present invention is not particularly limited the pressure generating equipment of described the second reaction, with vaccum-pumping equipment well known to those skilled in the art; The present invention is not particularly limited other conditions of reaction, for guaranteeing that reaction process is steady, preferably in reaction process, stirs; The present invention is not particularly limited the mode stirring, with alr mode well known to those skilled in the art.
The present invention, after obtaining above-mentioned dihydroxyphenyl propane formaldehyde epoxy resin, for further improving the purity of dihydroxyphenyl propane formaldehyde epoxy resin, reduces the hydrolyzable chlorine content in dihydroxyphenyl propane formaldehyde epoxy resin, and the dihydroxyphenyl propane formaldehyde epoxy resin preferably above-mentioned steps being obtained is refined.The present invention is not particularly limited refining method, with dihydroxyphenyl propane formaldehyde epoxy resin process for purification well known to those skilled in the art, preferably according to following steps, carry out, under the effect of the second basic catalyst, the dihydroxyphenyl propane formaldehyde epoxy resin that above-mentioned steps is obtained is dissolved in organic solvent and carries out the 3rd reaction, obtains refining dihydroxyphenyl propane formaldehyde epoxy resin.
The temperature of described the 3rd reaction is preferably 60~90 ℃, more preferably 70~80 ℃; The time of described the 3rd reaction is preferably 1~3 hour, more preferably 1.5~2.5 hours; Described organic solvent is preferably ethylene glycol, toluene, ethylbenzene, dimethylbenzene, Virahol, methylethylketone or methyl iso-butyl ketone (MIBK), more preferably toluene, methyl iso-butyl ketone (MIBK) or Virahol; The mass ratio of described organic solvent and dihydroxyphenyl propane formaldehyde epoxy resin is preferably (2~8): 1, more preferably (3~7): 1.
Described the second basic catalyst is preferably KOH solution, K
2cO
3solution, NaOH solution, Na
2cO
3one or more in solution, more preferably KOH solution, K
2cO
3solution, NaOH solution or Na
2cO
3, most preferably be KOH solution or NaOH solution; Described the second basic catalyst mass concentration is preferably 30~50%, and more preferably 45~50%; In described the second basic catalyst, the mass ratio of solute and dihydroxyphenyl propane formaldehyde epoxy resin is preferably (0.01~0.1): 1, more preferably (0.025~0.06): 1.
The present invention is not particularly limited the pressure of above-mentioned the 3rd reaction, with the pressure of dihydroxyphenyl propane formaldehyde epoxy resin refining reaction well known to those skilled in the art; The present invention is not particularly limited other conditions of above-mentioned reaction, preferably, after refining reaction finishes, adds deionized water to wash, and filters, and finally sloughs organic solvent and obtains refining dihydroxyphenyl propane formaldehyde epoxy resin.The present invention is not particularly limited deionized water, with the deionized water for washing well known to those skilled in the art; The present invention is not particularly limited the method for filtering, with filter method well known to those skilled in the art; The present invention is not particularly limited sloughing the method for organic solvent, with the method for desolventizing well known to those skilled in the art.
In the present invention, the performance index of the dihydroxyphenyl propane formaldehyde epoxy resin preparing, all detect according to the method for national Specification.
Technical requirements according to the mensuration > > of national standard < < GB/T4612-2008 plastic hoop oxygen compound epoxy equivalent (weight) detects the epoxy equivalent (weight) of dihydroxyphenyl propane formaldehyde epoxy resin;
According to the mensuration part 1 of national standard < < GB/T4618.1-2008 plastic hoop epoxy resins cl content: the technical requirements of inorganic chlorine > > detects the content of inorganic chlorine of dihydroxyphenyl propane formaldehyde epoxy resin;
According to the mensuration part 2 of national standard < < GB/T4618.2-2008 plastic hoop epoxy resins cl content: easily the technical requirements of saponification chlorine > > detects the hydrolyzable chlorine content of dihydroxyphenyl propane formaldehyde epoxy resin;
Colourity according to the technical requirements dihydroxyphenyl propane formaldehyde epoxy resin of national standard < < GB/T22295-2008 color of transparent liquids measuring method (Gardner's colourity) > > detects.
To using the dihydroxyphenyl propane formaldehyde epoxy resin that aforesaid method of the present invention prepares to detect, result shows, epoxy equivalent (weight) content is 196.0g/eq, and hydrolyzable chlorine content is 65.0ppm, and content of inorganic chlorine is 0.86ppm, and colourimetric number is 1.
The present invention also provides a kind of copper-clad laminate, comprises Copper Foil, glass-fiber-fabric and is solidificated in the composition epoxy resin on described glass-fiber-fabric, comprises the dihydroxyphenyl propane formaldehyde epoxy resin that aforesaid method prepares in described composition epoxy resin.The present invention is not particularly limited the preparation method of described copper-clad laminate, and with preparation method well known to those skilled in the art, in the present invention, concrete grammar preferably carries out according to following steps:
By described dihydroxyphenyl propane formaldehyde epoxy resin, dimethyl formamide (DMF), 2-ethyl-4-methylimidazole (2E4MZ) and phenol resol (SH-1107, Shandong holy well Chemical Co., Ltd., 107 ℃ of softening temperatures) mix, stir, obtain composition epoxy resin.
Above-mentioned composition epoxy resin being immersed on the glass-fiber-fabric of 100 μ m, is that 150 ℃ of baking oven inner dryings obtained prepreg after 5 minutes in temperature again.
Then 5 above-mentioned prepregs are overlapping, lower surface respectively adds the Copper Foil that a slice thickness is 18 μ m thereon, and in temperature, being 175 ℃ is 25Kg/cm with pressure
2condition under, heating and pressurizing obtained copper-clad laminate after 140 minutes.
The quality of described dimethyl formamide (DMF) and the mass ratio of composition epoxy resin are 0.5:1; The mass ratio 0.002:1 of described 2-ethyl-4-methylimidazole and dihydroxyphenyl propane formaldehyde epoxy resin; In described phenol resol, in the mole number of hydroxyl and dihydroxyphenyl propane formaldehyde epoxy resin, the ratio of the mole number of epoxy group(ing) is 1:1.
To using the copper-clad laminate that aforesaid method of the present invention prepares to detect, result shows, the glass transformation temperature of copper-clad laminate is 181 ℃, and peel strength of copper foil is 1.5N/mm.
In order further to understand the present invention, below in conjunction with embodiment, preparation method and the copper-clad laminate of a kind of dihydroxyphenyl propane formaldehyde epoxy resin provided by the invention are described, protection scope of the present invention is not limited by the following examples.
Comparative example 1
First 150g dihydroxyphenyl propane formaldehyde resin (SH-2130 type, Shandong holy well group, 130 ℃ of softening temperatures) and 1800g epoxy chloropropane are put into 2L reaction flask, stir at normal temperatures 30min.Then add 2.25g benzyltriethylammoinium chloride, and reaction flask is heated to 75 ℃, carry out the first reaction, react after 4 hours, obtain the first reaction mixture.
Then reaction flask is vacuumized, vacuum tightness is 0.05Mpa, reduced-pressure backflow at 75 ℃, and be 50% NaOH solution to dripping 75g mass concentration in the first reaction mixture in reaction flask, after 4 hours, dropwise, reaction finishes and reclaims epoxy chloropropane, obtains the thick product of dihydroxyphenyl propane formaldehyde epoxy resin.
The last NaOH solution that is 15% by the thick product of above-mentioned dihydroxyphenyl propane formaldehyde epoxy resin, 500g toluene solvant and 13g mass concentration again mixes, at 70 ℃, carry out refining reaction, react after 2 hours, then obtain refining dihydroxyphenyl propane formaldehyde epoxy resin through deionized water washing, filtration, desolventizing.
The dihydroxyphenyl propane formaldehyde epoxy resin that aforesaid method is prepared detects, and result shows, epoxy equivalent (weight) content is 195.0g/eq, and hydrolyzable chlorine content is 300.0ppm, and content of inorganic chlorine is 0.80ppm, and colourimetric number is 4.0.
Dihydroxyphenyl propane formaldehyde epoxy resin 200g prepared by aforesaid method mixes with 309g dimethyl formamide (DMF), 0.4g2-ethyl-4-methylimidazole (2E4MZ), 108.7g phenol resol, stirs, and obtains composition epoxy resin.
Above-mentioned composition epoxy resin is immersed on the glass-fiber-fabric that thickness is 100 μ m again, at the baking oven inner dryings of 150 ℃, after 5 minutes, obtains prepreg.
Then 5 above-mentioned prepregs are overlapping, lower surface respectively adds the Copper Foil that a slice thickness is 18 μ m thereon, is heated to 175 ℃, then at 25Kg/cm
2pressure under pressurize, be 140 minutes clamping time, finally obtains copper-clad laminate 1#.
Embodiment 1
First by 150g dihydroxyphenyl propane formaldehyde resin (SH-2130 type, Shandong holy well group, 130 ℃ of softening temperatures), 555g epoxy chloropropane and 1g zinc powder are put into 2L reaction flask, stir at normal temperatures 30min.Then reaction flask is vacuumized, vacuum tightness is 0.03Mpa, then passes into high pure nitrogen in reaction flask, displacement surplus air, and so repeatable operation is 2 times.Finally pass into high pure nitrogen to normal pressure, add 2.25g benzyltriethylammoinium chloride, and reaction flask is heated to 70 ℃, carry out the first reaction, react after 4 hours, obtain the first reaction mixture.
Then reaction flask is vacuumized, vacuum tightness is 0.025Mpa, reduced-pressure backflow at 70 ℃, and be 50% NaOH solution to dripping 105g mass concentration in the first reaction mixture in reaction flask, after 4 hours, dropwise, reaction finishes and reclaims epoxy chloropropane, obtains the thick product of dihydroxyphenyl propane formaldehyde epoxy resin.
The last NaOH solution that is 15% by the thick product of above-mentioned dihydroxyphenyl propane formaldehyde epoxy resin, 500g toluene solvant and 19g mass concentration again mixes, at 70 ℃, carry out refining reaction, react after 2 hours, then obtain refining dihydroxyphenyl propane formaldehyde epoxy resin through deionized water washing, filtration, desolventizing.
The dihydroxyphenyl propane formaldehyde epoxy resin that aforesaid method of the present invention is prepared detects, and result shows, epoxy equivalent (weight) content is 206.0g/eq, and hydrolyzable chlorine content is 72.1ppm, and content of inorganic chlorine is 0.68ppm, and colourimetric number is 1.0.
Dihydroxyphenyl propane formaldehyde epoxy resin 200g prepared by aforesaid method of the present invention mixes with 303g dimethyl formamide (DMF), 0.4g2-ethyl-4-methylimidazole (2E4MZ), 102.9g phenol resol, stirs, and obtains composition epoxy resin.
Above-mentioned composition epoxy resin is immersed on the glass-fiber-fabric that thickness is 100 μ m again, at the baking oven inner dryings of 150 ℃, after 5 minutes, obtains prepreg.
Then 5 above-mentioned prepregs are overlapping, lower surface respectively adds the Copper Foil that a slice thickness is 18 μ m thereon, is heated to 175 ℃, then at 25Kg/cm
2pressure under pressurize, be 140 minutes clamping time, finally obtains copper-clad laminate 1.
Embodiment 2
First by 120g dihydroxyphenyl propane formaldehyde resin (SH-2130 type, Shandong holy well group, 130 ℃ of softening temperatures), 601g epoxy chloropropane and 2g iron powder are put into 2L reaction flask, stir at normal temperatures 30min.Then reaction flask is vacuumized, vacuum tightness is 0.030Mpa, then passes into high pure nitrogen in reaction flask, displacement surplus air, and so repeatable operation is 3 times.Finally pass into high pure nitrogen to normal pressure, add 3.2g benzyl trimethyl ammonium chloride, and reaction flask is heated to 60 ℃, carry out the first reaction, react after 5 hours, obtain the first reaction mixture.
Then reaction flask is vacuumized, vacuum tightness is 0.035Mpa, reduced-pressure backflow at 72 ℃, and be 50% NaOH solution to dripping 81.6g mass concentration in the first reaction mixture in reaction flask, after 4.5 hours, dropwise, reaction finishes and reclaims epoxy chloropropane, obtains the thick product of dihydroxyphenyl propane formaldehyde epoxy resin.
The last NaOH solution that is 20% by the thick product of above-mentioned dihydroxyphenyl propane formaldehyde epoxy resin, 450g isopropanol solvent and 18g mass concentration again mixes, at 75 ℃, carry out refining reaction, react after 2 hours, then obtain refining dihydroxyphenyl propane formaldehyde epoxy resin through deionized water washing, filtration, desolventizing.
The dihydroxyphenyl propane formaldehyde epoxy resin that aforesaid method of the present invention is prepared detects, and result shows, epoxy equivalent (weight) content is 196.0g/eq, and hydrolyzable chlorine content is 65.0ppm, and content of inorganic chlorine is 0.86ppm, and colourimetric number is 1.0.
Dihydroxyphenyl propane formaldehyde epoxy resin 200g prepared by aforesaid method of the present invention mixes with 308g dimethyl formamide (DMF), 0.4g2-ethyl-4-methylimidazole (2E4MZ), 108.2g phenol resol, stirs, and obtains composition epoxy resin.
Above-mentioned composition epoxy resin is immersed on the glass-fiber-fabric that thickness is 100 μ m again, at the baking oven inner dryings of 150 ℃, after 5 minutes, obtains prepreg.
Then 5 above-mentioned prepregs are overlapping, lower surface respectively adds the Copper Foil that a slice thickness is 18 μ m thereon, is heated to 175 ℃, then at 25Kg/cm
2pressure under pressurize, be 140 minutes clamping time, finally obtains copper-clad laminate 2.
Embodiment 3
First by 120g dihydroxyphenyl propane formaldehyde resin (SH-2130 type, Shandong holy well group, 130 ℃ of softening temperatures), 350g epoxy chloropropane and 1g Na
2sO
3put into 2L reaction flask, stir at normal temperatures 30min.Then reaction flask is vacuumized, vacuum tightness is 0.030Mpa, then passes into high pure nitrogen in reaction flask, displacement surplus air, and so repeatable operation is 4 times.Finally pass into high pure nitrogen to normal pressure, add 3g trityl group bromo-phosphonium, and reaction flask is heated to 76 ℃, carry out the first reaction, react after 4 hours, obtain the first reaction mixture.
Then reaction flask is vacuumized, vacuum tightness is 0.026Mpa, reduced-pressure backflow at 70 ℃, and be 50% KOH solution to dripping 114g mass concentration in the first reaction mixture in reaction flask, after 5 hours, dropwise, reaction finishes and reclaims epoxy chloropropane, obtains the thick product of dihydroxyphenyl propane formaldehyde epoxy resin.
The last KOH solution that is 20% by the thick product of above-mentioned dihydroxyphenyl propane formaldehyde epoxy resin, 550g methyl isobutyl ketone solvent and 11g mass concentration again mixes, at 75 ℃, carry out refining reaction, react after 2 hours, then obtain refining dihydroxyphenyl propane formaldehyde epoxy resin through deionized water washing, filtration, desolventizing.
The dihydroxyphenyl propane formaldehyde epoxy resin that aforesaid method of the present invention is prepared detects, and result shows, epoxy equivalent (weight) content is 210.0g/eq, and hydrolyzable chlorine content is 51.0ppm, and content of inorganic chlorine is 0.50ppm, and colourimetric number is 1.0.
Dihydroxyphenyl propane formaldehyde epoxy resin 200g prepared by aforesaid method of the present invention mixes with 301g dimethyl formamide (DMF), 0.4g2-ethyl-4-methylimidazole (2E4MZ), 101g phenol resol, stirs, and obtains composition epoxy resin.
Above-mentioned composition epoxy resin is immersed on the glass-fiber-fabric that thickness is 100 μ m again, at the baking oven inner dryings of 150 ℃, after 5 minutes, obtains prepreg.
Then 5 above-mentioned prepregs are overlapping, lower surface respectively adds the Copper Foil that a slice thickness is 18 μ m thereon, is heated to 175 ℃, then at 25Kg/cm
2pressure under pressurize, be 140 minutes clamping time, finally obtains copper-clad laminate 3.
Embodiment 4
By copper-clad laminate 1# and the prepared copper-clad laminate 1~3 of embodiment 1~3 of comparative example 1 preparation, according to the method tested glass invert point of 2.4.25 defined in IPC-TM-650 testing method handbook, method test peel strength of copper foil according to 2.4.8 defined in IPC-TM-650 testing method handbook, the results are shown in Table 1.
The glass transition temp of table 1 copper-clad laminate 1# and copper-clad laminate 1~3 and peel strength of copper foil
As can be seen from Table 1, in the embodiment of the present invention 1~3, the glass transformation temperature of the copper-clad laminate 1~3 of preparation is greater than 178 ℃, has higher glass transformation temperature, thereby has good thermotolerance.
Above the preparation method of a kind of dihydroxyphenyl propane formaldehyde epoxy resin 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.