CN101643525B - Epoxy resin and preparation method thereof - Google Patents
Epoxy resin and preparation method thereof Download PDFInfo
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- CN101643525B CN101643525B CN2009101897329A CN200910189732A CN101643525B CN 101643525 B CN101643525 B CN 101643525B CN 2009101897329 A CN2009101897329 A CN 2009101897329A CN 200910189732 A CN200910189732 A CN 200910189732A CN 101643525 B CN101643525 B CN 101643525B
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- para hydroxybenzene
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Abstract
The invention relates to an epoxy resin and a preparation method thereof. The epoxy resin has the following structural formula (I). The preparation method can adopt a one-step method, namely directly condensing the mixture of hydroxystyrene/styrene copolymer and epihalohydrin in the presence of alkali to obtain the epoxy resin, and also can adopt a two-step method, namely firstly etherifying the hydroxystyrene/styrene copolymer and epihalohydrin in the presence of catalysts and then closing loop in the presence of alkali liquor. The epoxy resin of the invention has high heat resistance, low dielectric constant and low dielectric dissipation factors, thus being used for manufacturing the resin sheets, resin composition copper foils, the prepregs, the laminate and the printed circuit boards. R is shown in (II), and n and m are natural numbers.
Description
Technical field
The present invention relates to a kind of resin and preparation method thereof, relate in particular to a kind of polyfunctional epoxy resin and preparation method thereof.
Background technology
The existing material that is used for tellite, the epoxy resin that the adhesion properties that is widely used is excellent.Epoxy resin is to contain two or more epoxide groups in the general reference molecule; With organic cpds such as aliphatics, alicyclic or aromatic series is skeleton, and can in the presence of suitable chemical reagent (solidifying agent), react the general name of the compound of the three-dimensional netted cured article of generation through epoxide group.It is one of kind important in the thermoset macromolecule material.Epoxy resin is owing to have good chemicalstability, electrical insulating property, erosion resistance, cohesiveness and physical strength thereby be widely used in fields such as tackiness agent, coating, veneer sheet, moulding material, cast material, tellite.
In recent years, along with the development of computingmachine and information communication device high performance, multifunction and networking, for high-speed transfer and processing large vol information, operation signal trends towards high frequencyization, thereby the material of circuit substrate has been proposed requirement.These requirements comprise: 1, excellent dielectric properties (promptly low specific inductivity and low medium consumption factor), and can under the temperature of relative broad range and frequency condition, keep stable; 2, can anti-PCB course of processing soda acid, high temperature and high humidity environment impact and the moisture absorption does not take place expand so that the layering explosion; 3, processing and the mounting process requirement under the adaptation high temperature.More than requirement needs epoxy resin in high humidity environment, to guarantee lower water-intake rate, lower polarity.
Yet, general specific inductivity of common epoxy resin circuit substrate (FR-4 copper-clad plate) and dielectric loss angle tangent higher (specific inductivity 4.4, dielectric loss angle tangent about 0.02), high frequency characteristics is insufficient, requirement that can not the adaptation signal high frequencyization.
Therefore, set about with thermotolerance, humidity resistance aspect from giving epoxy resin itself, the epoxy resin of development of new structure is inevitable approach.After in epoxy resin, introducing the group that stiff chain is big, hydrophobicity is strong through the method for modification, can keep superior heat resistance can reduce water-intake rate again.The work of this respect all can improve the thermotolerance and the humidity resistance of curable epoxide thing greatly as in epoxy resin, introducing structures such as naphthalene nucleus, NSC 7352, biphenyl.But on reduction specific inductivity and dielectric loss, also need further to introduce low polar group and could obtain better dielectric characteristics.
Summary of the invention
The object of the present invention is to provide a kind of epoxy resin, it makes this resin have higher thermostability and humidity resistance, and has better dielectric characteristics through introducing low polarity vinylbenzene structure.
Another object of the present invention provides a kind of preparation method of epoxy resin, and this method is simple to operate, by the epoxy resin of its preparation, has higher thermostability, humidity resistance and dielectric characteristics.For realizing above-mentioned purpose, the present invention provides a kind of epoxy resin, and it has following molecular structural formula (I):
Wherein R is:
n and m are natural number, m/n=0.8～19.
Epoxy resin of the present invention can obtain through following reaction:
Wherein
X is: Br or Cl or I or F;
R is:
N and m are natural number, m/n=0.8～19.
The present invention also provides a kind of preparation method of epoxy resin, and it is through para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin etherificate under the effect of catalyzer, and closed loop obtains epoxy resin under the effect of alkali lye then, and it specifically comprises the steps:
Step 1; Under the inert nitrogen gas protection; In para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin, add catalyzer, carry out etherification reaction 50-120 ℃ of heating, wherein para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin mol ratio are: 1: 1～20;
Step 2; Etherification reaction finishes back dropping alkaline solution and carries out ring-closure reaction, reacts 1～5 hour down at 80-120 ℃, and the add-on of alkali lye is that para hydroxybenzene ethylene/styrene multipolymer is 1～2: 1 in molar ratio; After reaction finishes through filtering; Washing removes freshen, and excessive epihalohydrin is removed in underpressure distillation, obtains containing the polyfunctional epoxy resin of low polarity vinylbenzene structure at last.
The present invention also provides the another kind of method for preparing epoxy resin; Its adopt single stage method preparation be para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin mixture directly under the effect of alkali condensation obtain epoxy resin; Its concrete steps are: organic solvent, para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin are mixed, and para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin feed intake by 1: 1～20 mol ratio, under protection of inert gas 50-150 ℃ of reacting by heating 1～5 hour; The while dripping alkali liquid; The mol ratio of alkali lye and para hydroxybenzene ethylene/styrene multipolymer is 1～2: 1, and through filtering, washing removed freshen after reaction finished; Excessive epihalohydrin is removed in underpressure distillation, obtains containing the polyfunctional epoxy resin of low polarity vinylbenzene structure at last.
The invention has the beneficial effects as follows: epoxy resin of the present invention; It contains the low vinylbenzene structure of polarity; Therefore the dielectric properties of this resin have obtained optimization, specific inductivity is compared with general epoxy resin with dielectric loss angle tangent, the reduction that has obtained; Along with the increase of styrene units content in the structure, specific inductivity and dielectric loss angle tangent are littler.The present invention prepares the method for epoxy resin, and it is simple to operate, by the epoxy resin of its preparation, has higher thermostability and humidity resistance.
Embodiment
Novel low polarity vinylbenzene structural epoxy resins provided by the invention, it has following molecular structural formula (I):
Wherein R is:
n and m are natural number, m/n=0.8～19.
The multi-group epoxy compound that the present invention contains low polarity vinylbenzene structure is to use a kind of polyphenolic substance and epihalohydrin, and reaction obtains under inert atmosphere.
The polyphenolic substance that is used for making the epoxy resin that contains low polarity vinylbenzene structure among the present invention contains low polar vinylbenzene structure in structure, this polyphenolic substance is a kind of unsaturated phenol and cinnamic multipolymer, and this unsaturated phenol is para hydroxybenzene ethene.Para hydroxybenzene ethylene/styrene multipolymer can be synthetic by known method, like JP61-275307, DongJin Woo, and Polymer47 (2006): 3287-3291, JungKiKim, Polymer47 (2006): the method described in the 5799-5809.Known para hydroxybenzene ethylene/styrene multipolymer commodity have the MARUKA LYNCUR CST of Japanese Maruzen Petrochemical Co., Ltd..The para hydroxybenzene ethylene/styrene multipolymer that uses among the present invention has following structural formula (II), wherein m/n=0.8～19.
Preferred Epicholorohydrin of the epihalohydrin that uses among the present invention and table bromhydrin are preferably Epicholorohydrin again; The inert atmosphere that uses is nitrogen.
The present invention provides a kind of preparation method of epoxy resin, and this method adopts single stage method, promptly the mixture thing of para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin directly under the effect of alkali condensation obtain epoxy resin.Its concrete steps are: organic solvent, para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin are mixed; Para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 1～20 mol ratio; Under protection of inert gas 50-150 ℃ of reacting by heating 1～5 hour, dripping alkali liquid simultaneously, the mol ratio of alkali lye and para hydroxybenzene ethylene/styrene multipolymer is 1～2: 1; After reaction finishes through filtering; Washing removes freshen, and excess epichlorohydrin is removed in underpressure distillation, obtains containing the polyfunctional epoxy resin of low polarity vinylbenzene structure at last.
Use therein alkali lye can adopt sodium hydroxide, Pottasium Hydroxide etc., and used alkali lye is preferably selected denseer solution for use, and preferred concentrations is between 20-50wt%.
The mol ratio of para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin is preferably 1: 2-15.
Representative examples of organic comprises ketone such as methyl ethyl ketone and MIBK; Hydro carbons such as toluene and YLENE, alcohols such as methyl alcohol, ethanol, primary alconol, cellosolve such as methylcyclohexane and ethyl cellosolve; Ethers such as diox and diethoxyethane, DMSO 99.8MIN. and N.
The present invention also provides a kind of preparation method of epoxy resin; This method adopts two step method; Promptly earlier with para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin etherificate under the effect of catalyzer, closed loop obtains epoxy resin under the effect of alkali lye then, specifically comprises following steps:
Step 1; Under the inert nitrogen gas protection; In para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin, add catalyzer, carried out etherification reaction 1～5 hour 50-120 ℃ of heating, wherein para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin mol ratio are: 1: 1～20.
Step 2; Etherification reaction finishes back dropping alkaline solution and carries out ring-closure reaction, reacts 1～5 hour down at 80-120 ℃, and the add-on of alkali lye is that para hydroxybenzene ethylene/styrene multipolymer is 1～2: 1 in molar ratio; After reaction finishes through filtering; Washing removes freshen, and excessive Epicholorohydrin is removed in underpressure distillation, obtains containing the polyfunctional epoxy resin of low polarity vinylbenzene structure at last.
Wherein in the step 1 mol ratio of para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin between 1: 1～20, preferred 1: 2-15.
Catalyzer can use choline and salt, triphenyl phosphorus hydrochlorate, ammonium salt etc., and ammonium salt can be selected from 4 bromide, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, tetraethylammonium bromide etc.
Use therein alkali lye can adopt sodium hydroxide, and used alkali lye such as Pottasium Hydroxide is preferably selected denseer solution for use, and preferred concentrations is between 20-50wt%.
More than the reaction formula of reaction is represented as follows:
Wherein
X:Br or Cl or I or F
R：
Through above-mentioned reaction, the structural formula (I) that contains the epoxy resin of low polarity vinylbenzene structure finally synthetic provided by the invention.
The number-average molecular weight (Wn) of the epoxy resin of structural formula among the present invention (I) is between 1000-50000, and this number-average molecular weight is through using THF as moving phase, using the gel permeation chromatography of polystyrene standard as stationary phase.
Epoxy resin shown in the structural formula of the present invention (I) is because contain the low vinylbenzene structure of polarity in the molecular structure; Therefore the dielectric properties of this resin have obtained optimization; Specific inductivity is compared with general epoxy resin with dielectric loss angle tangent; The reduction that has obtained, along with the increase of styrene units content in the structure, specific inductivity and dielectric loss angle tangent are littler.
Epoxy resin of the present invention is except being used as preparing resin sheet, resin complexes metal copper foil, prepreg, veneer sheet, copper-clad laminate, the printed circuit board; Also can be used for being used for making sizing agent, coating, matrix material, also can be used for building, aviation, boats and ships, automotive industry.
Following examples explanation each embodiment of the present invention.
Synthetic example 1:
Para hydroxybenzene ethylene/styrene multipolymer, Epicholorohydrin He diox are mixed, and para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 5 mol ratio.Diox is a para hydroxybenzene ethylene/styrene multipolymer weight ratio 1.89.It is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods, and Wn is 4300.Said mixture heats under nitrogen protection, and Heating temperature is at 80 degree, and constantly stirring; While dropping sodium solution; The concentration of used sodium hydroxide solution is 25wt%, and the mol ratio of sodium hydroxide and para hydroxybenzene ethylene/styrene multipolymer is 2/1, and alkali lye dropwised in 3 hours; Moisture in reaction process in the system and Epicholorohydrin azeotropic are constantly told from system, and the Epicholorohydrin after the layering returns system.Excessive Epicholorohydrin and diox are removed in underpressure distillation, in residuum, add mibk, through washing and removing by filter salinity, then make to be washed with water to neutrality, obtain epoxy resin (1).The Wn of epoxy resin (1) is 4900.
Synthetic example 2:
Para hydroxybenzene ethylene/styrene multipolymer, Epicholorohydrin and toluene are mixed, and para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 10 mol ratio.Diox is that para hydroxybenzene ethylene/styrene multipolymer weight ratio is 1.89.It is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods, and Wn is 30000.Said mixture heats under nitrogen protection, and Heating temperature is at 100 degree, and constantly stirring; While dropping sodium solution; The concentration of used sodium hydroxide solution is 25wt%, and the mol ratio of sodium hydroxide and para hydroxybenzene ethylene/styrene multipolymer is 2/1, and alkali lye dropwised in 2 hours; Moisture in reaction process in the system and Epicholorohydrin azeotropic are constantly told from system, and the Epicholorohydrin after the layering returns system.Excessive Epicholorohydrin and toluene are removed in underpressure distillation, in residuum, add mibk, through washing and removing by filter salinity, then make to be washed with water to neutrality, obtain epoxy resin (2).The Wn of epoxy resin (2) is 34000.
Synthetic example 3:
Add para hydroxybenzene ethylene/styrene multipolymer, Epicholorohydrin and tetraethylammonium bromide in the four-hole boiling flask together; Para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 8 mol ratio; The tetraethylammonium bromide consumption is 0.5% (mol ratio) of para hydroxybenzene ethylene/styrene multipolymer, and it is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods, and Wn is that 20000 said mixtures heat under nitrogen protection; Heating temperature is 90 degree; Reacted 3 hours, the sodium hydroxide solution that etherification reaction finishes back dropping 40wt% carries out the ring-closure reaction temperature of reaction in 110 degree, 3 hours reaction times.Reacted after-filtration, washing removes freshen, and excessive Epicholorohydrin is removed in underpressure distillation, obtains epoxy resin (3) at last.The Wn of epoxy resin (3) is 22000.
Synthetic example 4:
Add para hydroxybenzene ethylene/styrene multipolymer, Epicholorohydrin and benzyltriethylammoinium chloride in the four-hole boiling flask together; Para hydroxybenzene ethylene/styrene multipolymer and Epicholorohydrin feed intake by 1: 12 mol ratio; The benzyltriethylammoinium chloride consumption is 1% (mol ratio) of para hydroxybenzene ethylene/styrene multipolymer; It is synthetic that para hydroxybenzene ethylene/styrene multipolymer is pressed currently known methods, and Wn is 8500.Said mixture heats under nitrogen protection, and Heating temperature is 100 degree, reacts 2 hours, and the sodium hydroxide solution that etherification reaction finishes back dropping 40wt% carries out the ring-closure reaction temperature of reaction in 110 degree, 3 hours reaction times.Reacted after-filtration, washing removes freshen, and excessive Epicholorohydrin is removed in underpressure distillation, obtains epoxy resin (3) at last.The Wn of epoxy resin (3) is 10000.
Embodiment (1～4):
The epoxy resin of gained among the synthetic routine 1-4 is prepared the glue shown in the table one.Use 2116 type electronic-grade woven fiber glass fully to soak in this glue, and in 155 degree baking ovens, remove and desolvate, obtain the prepreg sample of B-stage.
The electrolytic copper foil of eight prepregs and two one ounce is superimposed together, carries out lamination through thermocompressor and obtain doublesided copperclad laminate.Lamination is following: 1, material temperature when 80-120 spends, heat-up rate be controlled at the 1.0-3.0 degree/minute; 2, pressure is set to 20kg/cm2; 3, solidification value is spent 190, and keeps this temperature 90 minutes.Respective performances is seen table one.
Comparative Examples 1:
Use 40 parts, 60 parts N695 of SMA3000 Zelan 338 and be aided with catalyzer 2-MI, use MEK120 part that above-claimed cpd is dissolved, and be modulated into the glue of appropriate viscosity.Use 2116 type electronic-grade woven fiber glass to soak into this glue, and in 155 degree baking ovens, remove and desolvate, obtain the prepreg sample of B-stage.
The electrolytic copper foil of eight prepregs and two one ounce is superimposed together, carries out lamination through thermocompressor and obtain doublesided copperclad laminate.Lamination is following: 1, material temperature when 80-120 spends, heat-up rate be controlled at the 1.0-3.0 degree/minute; 2, pressure is set to 20kg/cm2; 3, solidification value is spent 190, and keeps this temperature 90 minutes.Respective performances is seen table one.
Comparative Examples 2
Use 80 parts, 20 parts PSM4357 of DER530 resin and be aided with catalyzer 2-MI, use MEK100 part that above-claimed cpd is dissolved, and be modulated into the glue of appropriate viscosity.Use 2116 type electronic-grade woven fiber glass to soak into this glue, and in 155 degree baking ovens, remove and desolvate, obtain the prepreg sample of B-stage.
The electrolytic copper foil of eight prepregs and two one ounce is superimposed together, carries out lamination through thermocompressor and obtain doublesided copperclad laminate.Lamination is identical with Comparative Examples 1, and respective performances is seen table one.
Comparative Examples 3
Use 80 parts, 20 parts PSM4357 of HP7200 resin and be aided with catalyzer 2-MI, use MEK90 part that above-claimed cpd is dissolved, and be modulated into the glue of appropriate viscosity.Use 2116 type electronic-grade woven fiber glass to soak into this glue, and in 155 degree baking ovens, remove and desolvate, obtain the prepreg sample of B-stage.
The electrolytic copper foil of eight prepregs and two one ounce is superimposed together, carries out lamination through thermocompressor and obtain doublesided copperclad laminate.Lamination is seen table one with Comparative Examples 1 identical respective performances.
Table one
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Epoxy resin (1) | 80 | ||||||
| Epoxy resin (2) | 70 | ||||||
| Epoxy resin (3) | 60 | ||||||
| Epoxy resin (4) | 50 | ||||||
| ?DER530 | 25 | 80 | |||||
| ?N695 | 23 | 60 | |||||
| ?HP7200 | 20 | 80 | |||||
| ?SMA3000 | 40 | ||||||
| ?DDM | 10 | ||||||
| ?PSM4357 | 20 | 15 | 27 | 20 | 20 | ||
| ?2-MI | 0.065 | 0.065 | 0.065 | 0.065 | 0.065 | 0.065 | 0.0065 |
| ?MEK | 100 | 90 | 90 | 120 | 120 | 100 | 90 |
| Tg (degree) | 150 | 160 | 152 | 153 | 130 | 125 | 145 |
| Stripping strength (N/mm) | 1.3 | 1.3 | 1.4 | 1.2 | 1.0 | 1.1 | 1.2 |
| Specific inductivity | 4.1 | 4.0 | 4.0 | 4.1 | 4.2 | 4.4 | 4.3 |
| Dielectric loss factor | 0.008 | 0.009 | 0.008 | 0.010 | 0.013 | 0.020 | 0.018 |
| Anti-immersed solder property | Well | Well | Well | Well | Bubble | Well | Well |
| PCT water-intake rate (weight %) | 0.15 | 0.20 | 0.18 | 0.20 | 0.46 | 0.25 | 0.27 |
| Anti-immersed solder property (S) behind the PCT | ＞300 | ＞300 | ＞300 | ＞300 | 82 | ＞300 | ＞300 |
Annotate 1:
1, each component is all remembered with the solids content weight part in the table one;
2, DER530 is the bisphenol A-type bromination bifunctional epoxy resin of DOW;
3, N690 is the adjacent sylvan formaldehyde epoxy resin of DIC;
4, HP7200 is the NSC 7352 epoxy resin of DIC;
5, PSM4357 is the resol of Japan crowd Rong Huaxue;
6, SMA3000 is the Zelan 338 of Sartomer;
7, DDM is 4 of Huifeng Synthetic Material Co., Ltd., Jiangyin, 4 '-MDA.
Annotate 2:
1, second-order transition temperature (Tg): use the DSC test, measure according to the DSC testing method of IPC-TM-6502.4.25 defined;
2, stripping strength is tested according to " after the thermal stresses " experiment condition in the IPC-TM-6502.4.8 method;
3, specific inductivity and dielectric loss factor: according to the method test of IPC-TM-6502.5.5.9 defined;
4, the evaluation of anti-immersed solder property: it is to take out after 20 seconds in 288 ℃ the tin stove to be cooled to room temperature that copper-clad laminate is immersed in temperature, and then is impregnated in the tin stove 5 times repeatedly, through observing the anti-immersed solder property of ocular estimate;
5, measuring water absorption: copper-clad laminate is immersed in the copper etchant solution, removes surperficial Copper Foil and estimate substrate.Substrate is placed in the pressure cooker, and at 121 ℃, 2atm handled down after 1 hour, measured the water-intake rate of substrate;
6, anti-immersed solder property evaluation behind the PCT: copper-clad laminate is immersed in the copper etchant solution, removes surperficial Copper Foil and estimate substrate.Substrate is placed in the pressure cooker, and at 121 ℃, 2atm handles after 2 hours down, is immersed in temperature and is in 288 ℃ the tin stove, when base material occurs bubbling or writes down the corresponding time during division.Appearance foaming or layering can finish to estimate when base material surpasses 5 minutes also in the tin stove.
Can find out from table one, embodiments of the invention, low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all good.On the other hand, the low-k of comparative example, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all bad.
Epoxy resin shown in the structural formula of the present invention (I) uses separately; Perhaps mix the resin combination that forms when using with other epoxy resin, low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all good.This resin combination is coated in preimpregnation sheet material that obtains on the base material and the veneer sheet of making through this preimpregnation sheet material of lamination; Low-k, the low-dielectric loss factor, thermotolerance, anti-immersed solder property, wet fastness, humidity resistance and and the cohesiveness of Copper Foil all good, can be used as electronic machine and use printed circuit board.
In sum; Epoxy resin of the present invention, it contains the low vinylbenzene structure of polarity, so the dielectric properties of this resin have obtained optimization; Specific inductivity is compared with general epoxy resin with dielectric loss angle tangent; The reduction that has obtained, along with the increase of styrene units content in the structure, specific inductivity and dielectric loss angle tangent are littler.The present invention prepares the method for epoxy resin; It is simple to operate, by the epoxy resin of its preparation, has higher thermostability and humidity resistance; Epoxy resin by this method preparation; It can be used as preparing resin sheet, resin complexes metal copper foil, prepreg, veneer sheet, copper-clad laminate, printed circuit board, also can be used for being used for making sizing agent, coating, matrix material, also can be used for building, aviation, boats and ships, automotive industry.
The above; Be merely preferred embodiment of the present invention; For the person of ordinary skill of the art, can make other various corresponding changes and distortion, and all these changes and distortion all should belong to the protection domain of claim of the present invention according to technical scheme of the present invention and technical conceive.
Claims (4)
1. the preparation method of an epoxy resin is characterized in that, para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin be etherificate under the effect of catalyzer, and closed loop obtains epoxy resin under the effect of alkali lye then, and it specifically comprises the steps:
Step 1; Under the inert nitrogen gas protection; In para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin, add catalyzer, carry out etherification reaction 50-120 ℃ of heating, wherein para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin mol ratio are: 1: 1～20;
Step 2; Etherification reaction finishes back dropping alkaline solution and carries out ring-closure reaction, reacts 1～5 hour down at 80-120 ℃, and the add-on of alkali lye is that para hydroxybenzene ethylene/styrene multipolymer is 1～2: 1 in molar ratio; After reaction finishes through filtering; Washing removes freshen, and excessive epihalohydrin is removed in underpressure distillation, obtains containing the polyfunctional epoxy resin of low polarity vinylbenzene structure at last;
This epoxy resin has following structural formula (I):
Wherein R is:
N and m are natural number;
Structural unit m/n=0.8～19 in the epoxy resin of structural formula (I), number-average molecular weight is between 1000-50000.
2. preparation method as claimed in claim 1 is characterized in that the mol ratio of para hydroxybenzene ethylene/styrene multipolymer and epihalohydrin is 1 in the said step 1: between the 2-15.
3. preparation method as claimed in claim 1; It is characterized in that; Said catalyzer comprises choline and salt, triphenyl phosphorus hydrochlorate, ammonium salt; Ammonium salt is selected from 4 bromide, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, cetyl trimethylammonium bromide, tetraethylammonium bromide, and described alkali lye adopts sodium hydroxide or Pottasium Hydroxide, and this concentration of lye is between 20-50wt%.
4. preparation side as claimed in claim 1 is characterized in that, employed epihalohydrin was an Epicholorohydrin during the epoxy resin of structural formula (I) was synthetic.
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| CN106905459A (en) * | 2015-12-22 | 2017-06-30 | 广东生益科技股份有限公司 | A kind of epoxy resin modification polystyrene resin, preparation method and its usage |
| CN108864341B (en) * | 2017-05-12 | 2020-10-13 | 湖北固润科技股份有限公司 | Poly (p-hydroxystyrene) epoxy resin, and synthesis and application thereof |
| CN109796728B (en) | 2019-01-30 | 2020-04-17 | 常州中英科技股份有限公司 | Polyphenol-modified hydrocarbon composition-based prepreg and copper-clad plate prepared from same |
| CN113025037A (en) * | 2021-02-09 | 2021-06-25 | 林州致远电子科技有限公司 | Thermosetting resin composition and preparation method and application thereof |
| CN113278251A (en) * | 2021-04-26 | 2021-08-20 | 厦门理工学院 | Epoxy resin for flexible circuit board, preparation method and device thereof, and computer equipment |
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