CN103694450A - Fire retardation epoxy resin and preparation method thereof - Google Patents
Fire retardation epoxy resin and preparation method thereof Download PDFInfo
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- CN103694450A CN103694450A CN201310573836.6A CN201310573836A CN103694450A CN 103694450 A CN103694450 A CN 103694450A CN 201310573836 A CN201310573836 A CN 201310573836A CN 103694450 A CN103694450 A CN 103694450A
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Abstract
The present invention provides a fire retardation epoxy resin and a preparation method thereof, wherein the fire retardation epoxy resin is represented by a formula (I), R1, R2 and R3 are independently selected from hydrogen or methyl, and n is a polymerization degree. Compared with the existing fire retardation additive, the fire retardation epoxy resin of the present invention has the following characteristics that: the fire retardation epoxy resin provides the fire retardation characteristic through the high benzene ring special structure, does not contain halogen, and does not require addition of other organic phosphorus-base fire retardation agents or other types of additives so as to provide good fire retardation, and due to no requirement of addition of any fire retardation agents, the curing product prepared from the fire retardation epoxy resin represented by the formula (I) has excellent performances of good mechanical property, good chemical stability, good moisture absorption resistance, low shrinkage during hardening, stable product size, and the like.
Description
Technical field
The invention belongs to resin material technical field, relate in particular to a kind of fire retarding epoxide resin and preparation method thereof.
Background technology
The advantages such as epoxy resin is good with its mechanical property, excellent insulation performance, bounding force is high, shrinking percentage is little, good stability and handling ease, and be widely used in the fields such as chemical industry, electron electric power, machinery, aerospace, coating, bonding.Yet the oxygen index of universal epoxy resin is only 19.8, belong to inflammable material.Along with the industries such as electronics, electrical equipment, coating are had higher requirement to its flame retardant resistance, a large amount of research has been carried out in countries in the world.
In recent decades, widely used in field of electronics is to take the brominated epoxy resin that tetrabromo-bisphenol is monomer, with bromine flame retardant epoxy cured article.Yet, brominated flame-retardant discharges toxic substance in burning or waste treatment, as produce a large amount of dense smoke and irritating toxic gas, produce the polybrominated dibenzo-furan (Toxic such as PBDF), dioxin (dioxin), probably carcinogenic and cause animal body deformity, process in addition or reclaim also suitable difficulty of brominated waste material." the electric and electronics offal treatment method (WEEE) " of European Union and " in electronic electric equipment restriction use some objectionable impurities instruction (RoHS) " draft for amendments, to the environment-friendly materials of halogen-free and lead-free standard in addition.
Along with growing to even greater heights of environmental protection cry, people are one after another in the alternative flame retardant products of finding environment-friendly and green, mainly by adopting additive flame retardant to realize.Adding flame-retardant and have the features such as simple process, raw material sources be extensive, is the flame resistant method of at present conventional epoxy resin.The additive flame retardant using at present can be divided into inorganic combustion inhibitor (comprising weighting agent) and organic fire-retardant.Conventional inorganic combustion inhibitor has aluminium hydroxide, hydrated aluminum oxide, magnesium hydroxide, boride, antimonous oxide, red phosphorus etc.; Organic fire-retardant comprises organic phosphorus flame retardant, mainly contains triphenylphosphate, Tritolyl Phosphate, trioctyl phosphate and three (chloroethyl) phosphoric acid ester etc.
But because the use of vast scale additive flame retardant can affect the mechanical property of material on the one hand, the performances such as second-order transition temperature (Tg), thermotolerance, processibility of cured article are reduced, adopt addition type phosphonium flame retardant also can cause the water-intake rate of epoxy resin to rise, moisture-resistance reduces; In curing and use procedure, the leakage gradually of fire retardant can cause flame retardant effect to reduce gradually, presents unsettled fire-retardant state on the other hand.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of fire retarding epoxide resin and preparation method thereof, and this fire retarding epoxide resin is self-antiflaming epoxy resin.
The invention provides a kind of fire retarding epoxide resin, as shown in the formula (I):
Wherein, R
1, R
2with R
3be selected from independently of one another hydrogen or methyl; N is the polymerization degree.
The present invention also provides a kind of preparation method of fire retarding epoxide resin, comprises the following steps:
A), by the resol shown in formula (II) and the compound that contains epoxy group(ing), under the effect of the first basic catalyst, heating, carries out pre-reaction; Then, under vacuum condition, add the second basic catalyst, carry out ring-closure reaction, obtain the fire retarding epoxide resin shown in formula (I); The described compound containing epoxy group(ing) is epoxy chloropropane and/or methyl epichlorohydrin;
Wherein, R
1, R
2with R
3be selected from independently of one another hydrogen or methyl; N is the polymerization degree.
Preferably, described pre-reaction also adds solubility promoter.
Preferably, described solubility promoter is selected from one or more in glycerol, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, polyoxyethylene glycol, propylene glycol monomethyl ether and caprolactone.
Preferably, the mass ratio of the resol shown in described formula (II) and solubility promoter is: 1:(0.01～0.1).
Preferably, described steps A) also comprise:
After ring-closure reaction, add organic solvent dissolution, carry out refining reaction under the effect of the 3rd basic catalyst, washing, after desolventizing, obtains the fire retarding epoxide resin shown in formula (I).
Preferably, described the first basic catalyst, the second basic catalyst and the 3rd basic catalyst are selected from one or more in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution independently of one another.
Preferably, the quality of described the first basic catalyst and the second basic catalyst and be 30%～70% of the resol quality shown in formula (II).
Preferably, the temperature of described pre-reaction is 40 ℃～70 ℃, and the time is 1～6h.
Preferably, the temperature of described ring-closure reaction is 40 ℃～70 ℃, and the time is 2～6h, and vacuum tightness is 0.01～0.06MPa.
The invention provides a kind of fire retarding epoxide resin and preparation method thereof, this fire retarding epoxide resin as shown in the formula (I), wherein, R
1, R
2with R
3be selected from independently of one another hydrogen or methyl; N is the polymerization degree.Compare with existing interpolation fire retardant, fire retarding epoxide resin of the present invention is to rely on the high phenyl ring special construction of self fire-retardant, not halogen-containing, and without the additive that adds other organic phosphorus flame retardants or other types, can have good flame retardant resistance; Meanwhile, due to without adding any fire retardant, the cured article that the fire retarding epoxide resin shown in formula (I) is made has good mechanical property, and chemical stability is good, and resistance to moisture absorption is good, during sclerosis, shrink little, the stable premium properties that waits of product size.
Experimental result shows, the thermally stratified layer time of applying copper-clad plate prepared by the fire retarding epoxide resin shown in formula of the present invention (I) is greater than 60min, and thermolysis calibration can reach 376 ℃, and water-absorbent is only 0.1%.。
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the fire retarding epoxide resin shown in the formula (I) preparing in the embodiment of the present invention 1;
Fig. 2 is the carbon-13 nmr spectra figure of the fire retarding epoxide resin shown in the formula (I) preparing in the embodiment of the present invention 1;
Fig. 3 is the infrared spectrogram of the fire retarding epoxide resin shown in the formula (I) preparing in the embodiment of the present invention 1.
Embodiment
The invention provides a kind of fire retarding epoxide resin, as shown in the formula (I):
Wherein, R
1, R
2with R
3be selected from independently of one another hydrogen or methyl; N is the polymerization degree, is preferably 0～20, more preferably 0～15.According to the present invention, described R
1, R
2with R
3can be hydrogen or methyl simultaneously, in the time of also can be different, there is no special restriction, preferably R
1, R
2with R
3be hydrogen or simultaneously for methyl simultaneously.
Fire retarding epoxide resin of the present invention is to rely on the high phenyl ring special construction of self fire-retardant, not halogen-containing, and without the additive that adds other organic phosphorus flame retardants or other types, can have good flame retardant resistance; Meanwhile, due to without adding any fire retardant, the cured article that the fire retarding epoxide resin shown in formula (I) is made has good mechanical property, and chemical stability is good, and resistance to moisture absorption is good, during sclerosis, shrink little, the stable premium properties that waits of product size.
The present invention also provides the preparation method of the fire retarding epoxide resin shown in above-mentioned formula (I), comprise the following steps: A) by the resol shown in formula (II), mix with solubility promoter containing the compound of epoxy group(ing), under the effect of the first basic catalyst, heating, carries out pre-reaction; Then, under vacuum condition, add the second basic catalyst, carry out ring-closure reaction, obtain the fire retarding epoxide resin shown in formula (I); The described compound containing epoxy group(ing) is epoxy chloropropane and/or methyl epichlorohydrin;
Wherein, R
1, R
2with R
3be selected from independently of one another hydrogen or methyl; N is the polymerization degree.Described R
1, R
2, R
3all same as above with n, do not repeat them here.
The present invention does not have special restriction to the source of all raw materials, for commercially available.The weight-average molecular weight of the resol shown in described formula (II) is preferably 500～3500; Its softening temperature is preferably 35 ℃～80 ℃; Its viscosity is preferably 0.5～5p (150 ℃); Its epoxy equivalent (weight) is preferably 220～270g/eq.
By the resol shown in formula (II) and the compound that contains epoxy group(ing).Wherein, the resol shown in described formula (II) with containing the compound of epoxy group(ing) preferably according to mass ratio 1:(3～10) ratio mix, 1:(4～8 more preferably), then be preferably 1:(4～6).According to the present invention, for the resol shown in formula (II) is mixed better with the compound containing epoxy group(ing), preferably also add solubility promoter.Described solubility promoter is solubility promoter well known to those skilled in the art, there is no special restriction, is preferably one or more in glycerol, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, polyoxyethylene glycol, propylene glycol monomethyl ether and caprolactone in the present invention; Resol shown in described formula (II) and the mass ratio of solubility promoter are preferably 1:(0.01～0.1), 1:(0.04～0.08 more preferably).
After raw material mixes, under the effect of the first basic catalyst, heating, carries out pre-reaction.Wherein, described the first basic catalyst is catalyzer well known to those skilled in the art, there is no special restriction, and the present invention preferably adds the aqueous solution of basic catalyst, the aqueous solution of the first basic catalyst that more preferably concentration is 5%～50%; The kind of described the first basic catalyst is preferably one or more in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution.
Under the effect of the first basic catalyst, heating, carries out pre-reaction.The temperature of described pre-reaction is preferably 40 ℃～70 ℃, and more preferably 50 ℃～70 ℃, then be preferably 60 ℃～70 ℃; The time of described pre-reaction is preferably 1～6h, 1～5h more preferably, then be preferably 2～5h.
For reducing the generation of side reaction, described pre-reaction is preferably carried out under the condition of protection of inert gas, more preferably under the condition of nitrogen protection, carries out.
After pre-reaction finishes, under vacuum condition, add the second basic catalyst, carry out ring-closure reaction.Described the second basic catalyst is catalyzer well known to those skilled in the art, there is no special restriction, and the present invention preferably adds the aqueous solution of basic catalyst, the aqueous solution of the second basic catalyst that more preferably concentration is 5%～50%; The kind of described the second basic catalyst is preferably one or more in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution.
According to the present invention, the amount of described the first basic catalyst and the second basic catalyst is preferably added according to both quality with for 30%～70% ratio of the resol quality shown in formula (II), and more preferably 40%～60%; When the first basic catalyst and the second basic catalyst are the aqueous solution, the solid content sum that is preferably both is 30%～70% of the resol quality shown in formula (II), more preferably 40%～60%; Described the first basic catalyst and the second basic catalyst relationship between quality between the two there is no special restriction, according to the mass ratio of the first basic catalyst and the second basic catalyst, be preferably (0.08～0.8): 1 ratio is added, more preferably (0.1～0.5): 1, then be preferably (0.1～0.3): 1.
Under the condition of vacuum and the existence of the second basic catalyst, carry out ring-closure reaction.The temperature of described ring-closure reaction is preferably 40 ℃～70 ℃, and more preferably 50 ℃～70 ℃, then be preferably 60 ℃～70 ℃; Time is preferably 2～6h, more preferably 4～6h; Vacuum tightness is preferably 0.01～0.06MPa, more preferably 0.04～0.06MPa.
After ring-closure reaction, preferably the compound containing epoxy group(ing) through reclaim under reduced pressure, can reuse.
After ring-closure reaction, obtain the fire retarding epoxide resin shown in formula (I), but it is crude product, in order to obtain the fire retarding epoxide resin that purity is higher, after ring-closure reaction, preferably add organic solvent dissolution product, under the effect of the 3rd basic catalyst, carry out refining reaction, washing, after desolventizing, obtains the fire retarding epoxide resin shown in formula (I).
Described organic solvent is organic solvent well known to those skilled in the art, there is no special restriction, is preferably one or more in benzene,toluene,xylene, pimelinketone, methyl iso-butyl ketone (MIBK) and propyl carbinol in the present invention; The total dose that described organic solvent adds is preferably 2～8 times of the fire retarding epoxide resin quality shown in formula (I), more preferably 2～4 times.
Described the 3rd basic catalyst is catalyzer well known to those skilled in the art, there is no special restriction, and the present invention preferably adds the aqueous solution of basic catalyst, the aqueous solution of the first basic catalyst that more preferably concentration is 5%～50%; The kind of described the 3rd basic catalyst is preferably one or more in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution.
The present invention does not have special restriction to the add-on of the 3rd basic catalyst, and preferably its solid content is 1%～10% of the resol quality shown in formula (II), and more preferably 1%～3%.
With after organic solvent dissolution, under the effect of the 3rd basic catalyst, carry out refining reaction, the temperature of described refining reaction is preferably 60 ℃～90 ℃, and more preferably 70 ℃～90 ℃, then be preferably 75 ℃～85 ℃; The time of described refining reaction is preferably 1～6h, 2～5h more preferably, then be preferably 3～4h.
After refining reaction, washing, after desolventizing, obtains the fire retarding epoxide resin shown in formula (I).The method of wherein said washing and desolventizing is method well known to those skilled in the art, there is no special restriction.
Experimental result shows, the thermally stratified layer time of applying copper-clad plate prepared by the fire retarding epoxide resin shown in formula of the present invention (I) is greater than 60min, and thermolysis calibration can reach 376 ℃, and water-absorbent is only 0.1%.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of fire retarding epoxide resin provided by the invention and preparation method thereof is described in detail.
In following examples, reagent used is commercially available, and the resol shown in formula used (II) is the XYLOK resol that Shandong Shengquan Chemical Industry Co., Ltd. produces, and product type is SH-4071.
Embodiment 1
In the four-hole bottle with stirring, thermometer, add the resol shown in 175g formula (II), 701g epoxy chloropropane and 5g1,4-dioxane, under the condition of high pure nitrogen protection, heating for dissolving, then to add 12g massfraction be 50% the NaOH aqueous solution, after 60 ℃ of reaction 2h, under the condition of vacuum tightness 0.05MPa, adding 125g massfraction is 50% NaOH aqueous solution catalysis closed reaction, reaction 6h, reclaim under reduced pressure epoxy chloropropane; Then in product, add the NaOH aqueous solution that 260g toluene and 8g massfraction are 50%, 85 ℃ of reaction 3h, are washed to neutrality, and decompression desolventizing, obtains the fire retarding epoxide resin shown in formula (I).
Utilize nucleus magnetic resonance to analyze the fire retarding epoxide resin shown in the formula obtaining in embodiment 1 (I), analysis condition is: solvent C DCl
3, operating frequency 400MHz; Obtain its hydrogen nuclear magnetic resonance spectrogram, as shown in Figure 1; Obtain its carbon-13 nmr spectra figure, as shown in Figure 2.
Utilize infrared spectra to analyze the fire retarding epoxide resin shown in the formula obtaining in embodiment 1 (I), obtain its infrared spectrogram, as shown in Figure 3.
Utilize infrared spectra to analyze the epoxy equivalent (weight) of the fire retarding epoxide resin shown in the formula obtaining in embodiment 1 (I), obtaining its epoxy ought be 239.5g/eq.
Utilize softening temperature tester to test the fire retarding epoxide resin shown in the formula obtaining in embodiment 1 (I), obtaining its softening temperature is 49.2 ℃.
Fire retarding epoxide resin shown in the formula obtaining in embodiment 1 (I) is carried out to viscosity performance test, and obtaining its viscosity is 1.18p(150 ℃).
Embodiment 2
In the four-hole bottle with stirring, thermometer, add the resol shown in 140g formula (II) and 670g epoxy chloropropane, under the condition of high pure nitrogen protection, heating for dissolving, adding 15g massfraction is 50% the NaOH aqueous solution again, after 60 ℃ of reaction 5h, under the condition of vacuum tightness 0.05MPa, adding 132g massfraction is 50% NaOH aqueous solution catalysis closed reaction, reaction 4h, reclaim under reduced pressure epoxy chloropropane; Then in product, add the NaOH aqueous solution that 240g toluene and 8g massfraction are 50%, 85 ℃ of reaction 3h, are washed to neutrality, and decompression desolventizing, obtains the fire retarding epoxide resin shown in formula (I).
Utilize infrared spectra to analyze the epoxy equivalent (weight) of the fire retarding epoxide resin shown in the formula obtaining in embodiment 2 (I), obtaining its epoxy ought be 235.6g/eq.
Utilize softening temperature tester to test the fire retarding epoxide resin shown in the formula obtaining in embodiment 2 (I), obtaining its softening temperature is 46.3 ℃.
Fire retarding epoxide resin shown in the formula obtaining in embodiment 2 (I) is carried out to viscosity performance test, and obtaining its viscosity is 0.86p(150 ℃).
Fire retarding epoxide resin (general T G150) shown in the formula that embodiment 2 is obtained (I) is made copper-clad plate according to the component shown in table 1.
Utilize differential scanning calorimetry (DSC, ℃), according to the DSC method of IPC-TM-6502.4.25 defined, test, obtain its second-order transition temperature (Tg) as shown in table 2.
According to UL94 vertical combustion method, the flame retardant resistance of copper-clad plate is tested, obtain the results are shown in Table 2.
According to IPC-TM-6502.4.24.1, the thermally stratified layer time of copper-clad plate is tested, obtain the results are shown in Table 1.
According to IPC-TM-6502.4.24, the thermal expansivity of copper-clad plate is tested, obtained the results are shown in Table 2.
According to IPC-TM-6502.4.26, the heat decomposition temperature of copper-clad plate is tested, obtained the results are shown in Table 2.
According to IPC-TM-6502.6.2.1, the water-absorbent of copper-clad plate is tested, obtain the results are shown in Table 2.
Embodiment 3
In the four-hole bottle with stirring, thermometer, add the resol shown in 175g formula (II), 705g epoxy chloropropane and 7g1,4-dioxane, under the condition of high pure nitrogen protection, heating for dissolving, then to add 34g massfraction be 50% sodium bicarbonate aqueous solution, after 60 ℃ of reaction 5h, under the condition of vacuum tightness 0.04MPa, adding 160g massfraction is 50% sodium bicarbonate aqueous solution catalysis closed reaction, reaction 6h, reclaim under reduced pressure epoxy chloropropane; Then in product, add the sodium bicarbonate aqueous solution that 300g toluene and 8g massfraction are 50%, 85 ℃ of reaction 3h, are washed to neutrality, and decompression desolventizing, obtains the fire retarding epoxide resin shown in formula (I).
Utilize infrared spectra to analyze the epoxy equivalent (weight) of the fire retarding epoxide resin shown in the formula obtaining in embodiment 3 (I), obtaining its epoxy ought be 245.2g/eq.
Utilize softening temperature tester to test the fire retarding epoxide resin shown in the formula obtaining in embodiment 3 (I), obtaining its softening temperature is 54.2 ℃.
Fire retarding epoxide resin shown in the formula obtaining in embodiment 3 (I) is carried out to viscosity performance test, and obtaining its viscosity is 1.82p(150 ℃).
Embodiment 4
In the four-hole bottle with stirring, thermometer, add the resol shown in 140g formula (II) and 690g epoxy chloropropane, under the condition of high pure nitrogen protection, heating for dissolving, adding 10g massfraction is 50% the NaOH aqueous solution again, after 60 ℃ of reaction 4h, under the condition of vacuum tightness 0.06MPa, adding 121g massfraction is 50% NaOH aqueous solution catalysis closed reaction, reaction 4h, reclaim under reduced pressure epoxy chloropropane; Then in product, add the NaOH aqueous solution that 140g toluene, 140g propyl carbinol and 8g massfraction are 50%, 85 ℃ of reaction 3h, are washed to neutrality, and decompression desolventizing, obtains the fire retarding epoxide resin shown in formula (I).
Utilize infrared spectra to analyze the epoxy equivalent (weight) of the fire retarding epoxide resin shown in the formula obtaining in embodiment 4 (I), obtaining its epoxy ought be 237.8g/eq.
Utilize softening temperature tester to test the fire retarding epoxide resin shown in the formula obtaining in embodiment 4 (I), obtaining its softening temperature is 48.3 ℃.
Fire retarding epoxide resin shown in the formula obtaining in embodiment 4 (I) is carried out to viscosity performance test, and obtaining its viscosity is 1.02p(150 ℃).
Comparative example 1
Bisphenol-A phenolic epoxy resin (general T G150) is made to copper-clad plate according to the component shown in table 1.
Utilize differential scanning calorimetry (DSC, ℃), according to the DSC method of IPC-TM-6502.4.25 defined, test, obtain its second-order transition temperature (Tg) as shown in table 2.
According to UL94 vertical combustion method, the flame retardant resistance of copper-clad plate is tested, obtain the results are shown in Table 2.
According to IPC-TM-6502.4.24.1, the thermally stratified layer time of copper-clad plate is tested, obtain the results are shown in Table 1.
According to IPC-TM-6502.4.24, the thermal expansivity of copper-clad plate is tested, obtained the results are shown in Table 2.
According to IPC-TM-6502.4.26, the heat decomposition temperature of copper-clad plate is tested, obtained the results are shown in Table 2.
According to IPC-TM-6502.6.2.1, the water-absorbent of copper-clad plate is tested, obtain the results are shown in Table 2.
The component of table 1 copper-clad plate
Table 2 copper-clad plate performance test results
The above is only the preferred embodiment of the present invention; 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 make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a fire retarding epoxide resin, as shown in the formula (I):
Wherein, R
1, R
2with R
3be selected from independently of one another hydrogen or methyl; N is the polymerization degree.
2. a preparation method for fire retarding epoxide resin, is characterized in that, comprises the following steps:
A), by the resol shown in formula (II) and the compound that contains epoxy group(ing), under the effect of the first basic catalyst, heating, carries out pre-reaction; Then, under vacuum condition, add the second basic catalyst, carry out ring-closure reaction, obtain the fire retarding epoxide resin shown in formula (I); The described compound containing epoxy group(ing) is epoxy chloropropane and/or methyl epichlorohydrin;
Wherein, R
1, R
2with R
3be selected from independently of one another hydrogen or methyl; N is the polymerization degree.
3. preparation method according to claim 2, is characterized in that, described pre-reaction also adds solubility promoter.
4. preparation method according to claim 3, is characterized in that, described solubility promoter is selected from one or more in glycerol, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, polyoxyethylene glycol, propylene glycol monomethyl ether and caprolactone.
5. preparation method according to claim 3, is characterized in that, the mass ratio of the resol shown in described formula (II) and solubility promoter is: 1:(0.01～0.1).
6. preparation method according to claim 2, is characterized in that, described steps A) also comprise:
After ring-closure reaction, add organic solvent dissolution, carry out refining reaction under the effect of the 3rd basic catalyst, washing, after desolventizing, obtains the fire retarding epoxide resin shown in formula (I).
7. preparation method according to claim 2, it is characterized in that, described the first basic catalyst, the second basic catalyst and the 3rd basic catalyst are selected from one or more in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution independently of one another.
8. preparation method according to claim 2, is characterized in that, the quality of described the first basic catalyst and the second basic catalyst and be 30%～70% of the resol quality shown in formula (II).
9. preparation method according to claim 2, is characterized in that, the temperature of described pre-reaction is 40 ℃～70 ℃, and the time is 1～6h.
10. preparation method according to claim 2, is characterized in that, the temperature of described ring-closure reaction is 40 ℃～70 ℃, and the time is 2～6h, and vacuum tightness is 0.01～0.06MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023006005A1 (en) * | 2021-07-28 | 2023-02-02 | 华为技术有限公司 | Epoxy resin and preparation method therefor, and resin composition |
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