CN102030726A - Preparation method of 4,4'-biphenol diglycidyl ether - Google Patents
Preparation method of 4,4'-biphenol diglycidyl ether Download PDFInfo
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Abstract
The invention discloses a preparation method of 4,4'-biphenol diglycidyl ether. In the preparation method provided by the invention, 4,4'-biphenol and epichlorohydrin are used as raw materials to be synthesized by a two-step method under the effect of a heterogeneous catalyst. The preparation method comprises the following steps: firstly, carrying out a ring-opening etherifying reaction, then carrying out a ring-closing reaction, and in the alkalizing process, separating out water generated in the reaction by a water-separating technique, so that the reaction shifts to the right at equilibrium, and various hydrolysis secondary reactions in the system can be controlled. The product obtained by the technique has high epoxide equivalent and high yield, the technique has simple reaction steps and is convenient for posttreatment, and experimental results show that the epoxide number is 0.65-0.67, and the melting range is 159.1-160.4 DEG C.
Description
Technical field
The present invention counts fat for high-performance thermosetting a kind of new raw material midbody is provided, and is a kind of specifically 4, the preparation method of 4 '-'-biphenyl diphenol diglycidylether.
Background technology
4,4-'-biphenyl diphenol diglycidylether has characteristics such as good toughness, viscosity are low, fillibility height, is widely used in fields such as binding agent, powder coating, epoxy molding plastic, especially has a good application prospect in high-performance electronic plastic packaging field.
Resins, epoxy is a kind of thermoset macromolecule material of widespread use, has excellent physical and mechanical properties and electric property, and along with the develop rapidly of electronics leading-edge field, Resins, epoxy is used as electronic package material.Because the Resins, epoxy price is more cheap relatively, moulding process is simple, be fit to scale operation, reliability and metal and ceramic phase are worked as, therefore widespread use Resins, epoxy in the plastic package, 80%～90% (wherein Japan is almost whole) of at present external semiconducter device are replaced by epoxy resin encapsulating material.The Resins, epoxy of electronic-grade not only requires to have excellent thermotolerance, water absorbability and mechanical property, and requires to have high epoxy value.Because the packaged material of universal epoxy resin solidification can not satisfy the technical requirements of present electronic package material, for toughness and the thermotolerance that improves Resins, epoxy, can in its structure, introduce high rigid radical, the introducing of high rigid radical can obviously improve the thermotolerance and the mechanical property of polymkeric substance.Biphenyl group is exactly a kind of high rigid radical, can improve thermotolerance on the one hand, can reduce free volume on the other hand to improve toughness and to reduce water-absorbent.Simultaneously, its melt viscosity is low, and stopping property is good, the working temperature broad, the oven test proof does not chap, and its maximum feature is to have crystalline form, can provide good operability and flowability to packaged material thus, be a kind of good unicircuit packaged material.
Traditional preparation 4, the technology of 4 '-'-biphenyl diphenol diglycidylether mainly is to adopt the preparation of NaOH method, but in order to obtain the product of epoxy equivalent (weight) near theoretical value, adding mode to NaOH has strict requirement, and suitable loaded down with trivial details in the production aftertreatment, bring very big unfavorable factor to industrial production.
4, the structural formula of 4 '-'-biphenyl diphenol diglycidylether is as follows:
4, the synthetic single stage method and the two-step approach of being divided into of 4 '-'-biphenyl diphenol diglycidylether.
Single stage method refers to 4, and 4 '-'-biphenyl diphenol and epoxy chloropropane act on next step reaction at concentrated base (NaOH), and open loop etherificate and dehydrochlorination closed loop are carried out simultaneously.
Two-step approach is meant 4, and 4 '-'-biphenyl diphenol and epoxy chloropropane elder generation open loop etherificate add alkali then and make etherificate product closed loop.Relative single stage method, the color and luster that two-step approach has molecular weight control easily, narrow molecular weight distribution, the high and low chloride content of oxirane value and can improve resin, thus guarantee that neo-epoxy resin has the desired performance of electronic-grade.
In Resins, epoxy preparation technology, no matter be that single stage method or two-step approach all exist various side reactions to influence its quality product, especially the hydrolysis reaction in the reaction process influences the most serious.
Summary of the invention
The purpose of this invention is to provide that a kind of reactions steps is simple, productive rate is high, oxirane value is high, handle and be easy to 4, the preparation method of 4 '-'-biphenyl diphenol diglycidylether.
The present invention is made up of following steps:
Ring opening etherification reaction process: get 4,4 '-'-biphenyl diphenol, add 4, the epoxy chloropropane that 4 '-'-biphenyl diphenol weight is 16～25 times, add water-soluble stronger phase-transfer catalyst to system then, its add-on is 4,1% of 4 '-'-biphenyl diphenol weight, phase-transfer catalyst is selected from benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, logical nitrogen protection is carried out ring opening etherification reaction at 70～100 ℃, after the reaction needed 3～10 hours, with high performance liquid chromatography detection reaction raw material 4,4 '-'-biphenyl diphenol content is not more than mass percent 0.5%, and the beginning underpressure distillation goes out excessive epoxy chloropropane;
The ring-closure reaction process: in above-mentioned reaction system, add earlier non-polar organic solvent, add-on is 4,17～20 times of 4 '-'-biphenyl diphenol weight; Divide three times again and add the solid alkali powder, solid alkali is selected from solid sodium hydroxide or solid potassium hydroxide, the consumption of solid sodium hydroxide is 4,0.65 times of 4 '-'-biphenyl diphenol compound weight, the add-on of solid potassium hydroxide is 4,0.91 times of 4 '-'-biphenyl diphenol compound weight, continue reaction 1 hour down in 80 ℃, heat up, reflux dewatering is removed and is added the water that water that alkali brings into and reaction generate in the ring-closure reaction process, and constantly tells the water that reaction generates in the system with water-and-oil separator, dehydration reaction detected with high performance liquid chromatography after 5～11 hours, make 4,4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction, with tap water and deionized water wash mother liquor, wash out the phase-transfer catalyst in the organic system, inorganic salt, the cooling mother liquor is separated out product, filters or the whizzer separation, vacuum-drying promptly gets 4,4 '-'-biphenyl diphenol diglycidylether.
Can to be selected from atmospheric boiling point be 80～138 ℃ proportion toluene, benzene or the dimethylbenzene lighter than water to non-polar organic solvent in the described ring-closure reaction process, with the water that reacts generation in following the minutes water water-and-oil separator separation system.
Non-polar organic solvent can also be selected from the proportion ethylene dichloride bigger than water in the ring-closure reaction process, uses branch water water-and-oil separator and separates.
The present invention 4, and the preparation method of 4-'-biphenyl diphenol diglycidylether is by 4, and 4-'-biphenyl diphenol and epoxy chloropropane are that method is synthetic in two steps under the effect of phase catalyst for raw material.Key is to adopt dewatering process in the one step ring-closure reaction process of back.By in closed loop procedure, adopting the solvent refluxing dehydration method, reduced the hydrolytic side reactions in the reaction process, the purity and the yield of reaction final product all are improved.
Remaining epoxy chloropropane is removed in the underpressure distillation of the present invention elder generation, use other non-polar organic solvents instead and add the alkali closed loop again, in this reaction process, remove and add the water that water that alkali brings into and reaction generate in the ring-closure reaction process by the method that adopts the non-polar organic solvent reflux dewatering, hydrolytic side reactions is reduced greatly, and allow molecular balance move right, and various hydrolytic side reactions are controlled.Thereby improve yield, oxirane value and the purity of product.
The present invention is 4, in 4 '-'-biphenyl diphenol and the epoxy chloropropane ring opening etherification reaction process, strengthen the epoxy chloropropane consumption, allow it not only do reaction raw materials but also do reaction solvent, because the epoxy chloropropane add-on is 4,16～25 times of 4 '-'-biphenyl diphenol weight, can restrain the reaction of molecule interchain like this, avoid molecular chain to increase, make low-molecular weight compound smoothly, and have only n epoxy chloropropane: n4,4 '-'-biphenyl diphenol proportioning raw materials just can make reaction generate target product greater than theoretical value 2: 1 (mol ratio), otherwise can polymerization reaction take place.Simultaneously, speed of response and 4 have been quickened in the application of phase-transfer catalyst, and the transformation efficiency of 4 '-'-biphenyl diphenol improves yield.
The product epoxy equivalent (weight) height that the inventive method obtains, productive rate height, simple, the convenient post-treatment of reactions steps.Its experimental result shows that its oxirane value is 0.65～0.67,159.1～160.4 ℃ of melting ranges.
General 4, the reaction process of 4 '-'-biphenyl diphenol is as follows:
At first 4,4 '-'-biphenyl diphenol and epoxy chloropropane ring opening etherification reaction generate the chloropharin intermediate, and dehydrochlorination carries out closed loop under alkaline condition then, obtains 4,4 '-'-biphenyl diphenol diglycidylether, and reaction mechanism is as follows:
Also have following side reaction:
1. main some related hydrolysis reaction in the reaction process:
2. epoxy chloropropane and 4, the β addition of 4 '-'-biphenyl diphenol:
3. the further addition of intermediate product:
The present invention adopts the solvent refluxing dewatering process in the reaction closed loop procedure, reduced a, b hydrolytic side reactions, thereby the finished product purity is improved; Water also is the by product in the reaction process, and its minimizing also can make molecular balance move right, and the ultimate yield of product also is improved.
The finished product of the present invention prove that by this invented technology products therefrom be target product 4 by following physical and chemical testing, 4 '-'-biphenyl diphenol diglycidylether, and index such as purity all improves a lot, and experiment analysis results is as follows:
1. 4,4 '-'-biphenyl diphenol diglycidylether physical and chemical index and structural characterization
1.1 4,4 '-'-biphenyl diphenol diglycidylether physical and chemical index
4, the outward appearance of 4 '-'-biphenyl diphenol diglycidylether, the volatilization physical and chemical index that grades are measured with reference to HG2-741-72, and oxirane value press GB4612-84 and measured, and content of organic chloride press GB12007-89 mensuration, and content of inorganic chlorine is pressed GB4618-84 mensuration, the results are shown in Table 1.
Table 14, the main physical and chemical index of 4 '-'-biphenyl diphenol diglycidylether
| Project | Index |
| Outward appearance | The white solid powder |
| Purity, % | ≥99? |
| Oxirane value, eq100g -1 | 0.65～0.67? |
| Organochlorine, mg100g -1 | ＜40? |
| Inorganic chlorine, mg100g -1 | ＜20? |
| Fugitive constituent, % | ≤0.5? |
| Ash, % | ≤0.1? |
| Melting range, ℃ | 159.1～160.4? |
1.2 structured testing
With infrared spectra product structure is characterized, as shown in Figure 1.From the infrared spectrum analysis as can be known: 2927cm
-1, 2874cm
-1The place is the hydrocarbon stretching vibration of methylene radical; 1605cm
-1, 1500cm
-1Near absorption peak is the phenyl ring skeletal vibration; 1242cm
-1, 1036cm
-1The c-o-c of place stretching vibration; 909cm
-1Neighbouring is the characteristic absorbance of epoxy construction.
1.3 nmr analysis
As shown in Figure 2.Proton nmr spectra (1H-NMR)
Adopting TMS is interior mark, and CDCl is a solvent.Chemical shift δ: the peak between 2.772～4.279 is for being epoxide group; Chemical shift δ: the peak is a benzene ring structure between 6.962～7.479.
1.3 molecular mass test
As shown in Figure 3.With mass spectroscopy the molecular weight of product, the theoretical value of molecular mass is 298.12, the mass spectroscopy value is 299.1, conforms to substantially with theoretical value.
1.4 the test of product purity
As shown in Figure 4.(HPLC) measures product purity with high performance liquid chromatograph, and product purity 〉=99% meets service requirements.
1.5 Measurement of melting point and ultimate analysis
Use melting point detector that the fusing point of product is measured, the literature value melting range is 158～160 ℃, and measured value is 159.1～160.4 ℃, conforms to substantially with document.
4,4 '-'-biphenyl diphenol diglycidylether molecular formula is C
18H
18O
4, by ultimate analysis measured value (calculated value)/% be: C is 72.02% (72.5%); H is 6.03% (6.0%).Results of elemental analyses conforms to theoretical value.
2. 4, organic solvent reflux dewatering technology is to the influence of reaction in 4 '-'-biphenyl diphenol diglycidylether compound experiment
In one step of back ring-closure reaction process, add the water that water that alkali brings into and reaction generate in the system, and the alkaline environment that provides of the alkali that adds, all can make the reaction intermediate that the back reaction generates the hydrolysis of chlorine element and can't closed loop, finally form by product.This experiment is removed remaining epoxy chloropropane by first underpressure distillation, use other non-polar organic solvent instead and add alkali again, and in this ring-closure reaction process, adopt the organic solvent reflux dewatering to remove water in the system, this technology not only makes hydrolytic side reactions reduce greatly, and allow molecular balance move right, improve the yield and the purity of product.This technology is to 4, the influence of 4 '-'-biphenyl diphenol diglycidylether quality such as following table 2:
Dewatering process is to 4, the influence of 4 '-'-biphenyl diphenol diglycidylether quality such as following table 2:
By last table 2 as can be seen, the water that organic solvent reflux dewatering method is removed in the system is very favourable to reaction, and yield, purity and the oxirane value of product all improved a lot.NaOH adds the amount that affiliation increases reaction system water in the solution mode, not only increases dewatering time, and allows hydrolytic side reactions increase, so this requirement of experiment NaOH powder or KOH powder.
Description of drawings
Fig. 1 is a product 4 of the present invention, the infrared spectrogram of 4 '-'-biphenyl diphenol diglycidylether;
Fig. 2 is a product 4 of the present invention, the 1H-NMR figure of 4 '-'-biphenyl diphenol diglycidylether;
Fig. 3 is a product 4 of the present invention, the mass spectrum of 4 '-'-biphenyl diphenol diglycidylether;
Fig. 4 is a product 4 of the present invention, the liquid chromatogram of 4 '-'-biphenyl diphenol diglycidylether.
Embodiment
Embodiment 1:
Ring opening etherification reaction process: with 4; 4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 320 grams, phase-transfer catalyst benzyltriethylammoinium chloride 0.2 gram add and have in the there-necked flask of water trap; logical nitrogen protection; heat up in 80 ℃, reacted 5.0 hours, with high performance liquid chromatography detection reaction raw material 4; 4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 100 ℃, and vacuum tightness is 0.075MPa.
Ring-closure reaction process: add 400 gram toluene to system then, divide again and add 13 gram NaOH for three times, 80 ℃ the reaction 1 hour after, heat up and allow toluene under normal pressure, reflux in 110 ℃, and constantly tell the water that reaction generates in the system with following minute water water-and-oil separator, dehydration reaction detected with high performance liquid chromatography after 8 hours, made 4,4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction.Add tap water and deionized water to system and carry out heat and wash, remove inorganic salt, phase-transfer catalyst benzyltriethylammoinium chloride in the reaction system, and make that organochlorine and inorganic chlorine reach product requirement in the reaction system.The cooling mother liquor is separated out by product, filters out product, and oven dry is weighed as 29.0 grams, and melting range is 159.1～160.4 ℃, product purity 99.4% (high performance liquid phase area normalization method), and product yield 92.1% (with 4,4 '-'-biphenyl diphenol meter), the oxirane value actual measurement is 0.650.
Embodiment 2:
Ring opening etherification reaction process: with 4; 4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 400 grams, phase-transfer catalyst benzyltriethylammoinium chloride 0.2 gram add and have in the there-necked flask of water trap; logical nitrogen protection; heat up in 100 ℃, reacted 3.0 hours, with high performance liquid chromatography detection reaction raw material 4; 4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 100 ℃, and vacuum tightness is 0.075MPa.
Ring-closure reaction process: add 400 gram toluene and 13 gram NaOH to system then, 80 ℃ the reaction 1 hour after, heat up and allow refluxing toluene in 110 ℃, and constantly tell the water that reaction generates in the system with following minute water water-and-oil separator, react and detect with high performance liquid chromatography after 8 hours, make 4,4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction.Add tap water and deionized water to system and carry out heat and wash, remove inorganic salt, phase-transfer catalyst benzyltriethylammoinium chloride in the reaction system, and make that organochlorine and inorganic chlorine reach product requirement in the reaction system.The cooling mother liquor is separated out by product, filters out product, and oven dry is weighed as 29.8 grams, and melting range is 159.2～160.3 ℃, product purity 99.4% (high performance liquid phase area normalization method), and product yield 93.0% (with 4,4 '-'-biphenyl diphenol meter), the oxirane value actual measurement is 0.656.
Embodiment 3
Ring opening etherification reaction process: with 4; 4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 400 grams, phase-transfer catalyst benzyltriethylammoinium chloride 0.2 gram add and have in the there-necked flask of water trap; logical nitrogen protection; heat up in 90 ℃, reacted 4.0 hours, with high performance liquid chromatography detection reaction raw material 4; 4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 115 ℃, and vacuum tightness is 0.075MPa.
Ring-closure reaction process: add 400 gram toluene and 13 gram NaOH to system then, 80 ℃ the reaction 1 hour after, heat up and allow refluxing toluene also constantly tell the water that reaction generates in the system with following minute water water-and-oil separator in 110 ℃, react and detect with high performance liquid chromatography after 8 hours, make 4,4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction.Add tap water and deionized water to system and carry out heat and wash, remove inorganic salt, phase-transfer catalyst benzyltriethylammoinium chloride in the reaction system, and make that organochlorine and inorganic chlorine reach product requirement in the reaction system.
Embodiment 4:
Ring opening etherification reaction process: with 4; 4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 500 grams, phase-transfer catalyst benzyltriethylammoinium chloride 0.2 gram add and have in the there-necked flask of water trap; logical nitrogen protection; heat up in 80 ℃, reacted 5.0 hours, with high performance liquid chromatography detection reaction raw material 4; 4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 100 ℃, and vacuum tightness is 0.075Mpa.
Ring-closure reaction process: add 400 gram toluene and 13 gram NaOH to system then, 80 ℃ the reaction 1 hour after, heat up and allow refluxing toluene and constantly tell the water that reaction generates in the system with following water-and-oil separator in 110 ℃, react and detect with high performance liquid chromatography after 8 hours, make 4,4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction.Add tap water and deionized water to system and carry out heat and wash, remove inorganic salt, phase-transfer catalyst benzyltriethylammoinium chloride in the reaction system, and make that organochlorine and inorganic chlorine reach product requirement in the reaction system.The cooling mother liquor is separated out by product, filters out product, and oven dry is weighed as 29.7 grams, and melting range is 159.2～160.3 ℃, product purity 99.5% (high performance liquid phase area normalization method), and product yield 92.9% (with 4,4 '-'-biphenyl diphenol meter), the oxirane value actual measurement is 0.662.
Ring opening etherification reaction process: with 4,4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 400 grams, phase-transfer catalyst benzyltriethylammoinium chloride 0.2 gram add in the there-necked flask, logical nitrogen protection, heat up in 70 ℃, reacted 10 hours, with high performance liquid chromatography detection reaction raw material 4,4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); Beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 100 ℃, and vacuum tightness increases to and is 0.075Mpa.
Ring-closure reaction process: add 400 gram dimethylbenzene and 13 gram NaOH to system then, 80 ℃ the reaction 1 hour after, heat up and allow system reflux in 138 ℃, tell the water that reaction generates in the system by following oily water separation hydrophone, react and detect 4 with high performance liquid chromatography after 5 hours, 4-'-biphenyl diphenol diglycidylether product with content greater than 99 9%, stopped reaction.Carry out the heat washing to system adding tap water and deionized water, remove inorganic salt, phase-transfer catalyst in the reaction system, and making that organochlorine and inorganic chlorine reach product requirement in the reaction system, the cooling mother liquor is separated out by product, by filtering or whizzer is isolated product, oven dry is weighed as 29.8 grams, melting range is 159.1～160.3 ℃, product purity 99.3% (high performance liquid phase area normalization method), and product yield 93.1% is (with 4,4 '-'-biphenyl diphenol meter), the oxirane value actual measurement is 0.665.
Ring opening etherification reaction process: with 4; 4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 400 grams, phase-transfer catalyst benzyltriethylammoinium chloride 0.2 gram add in the there-necked flask; logical nitrogen protection; heat up in 80 ℃, reacted 5.0 hours, with high performance liquid chromatography detection reaction raw material 4; 4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 100 ℃, and vacuum tightness increases to and is 0.075Mpa.
Ring-closure reaction process: add 380 gram benzene and 13 gram NaOH to system then, 80 ℃ the reaction 1 hour after, benzene begins to reflux under this temperature, tell the water that reaction generates in the system by dividing water oily water separation hydrophone down, make 4 with the high performance liquid chromatography detection after 11 hours, 4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction.Carry out the heat washing to system adding tap water and deionized water, remove inorganic salt, phase-transfer catalyst in the reaction system, and making that organochlorine and inorganic chlorine reach product requirement in the reaction system, the cooling mother liquor is separated out by product, filters out product, oven dry is weighed as oven dry and is weighed as 29.9 grams, melting range is 159.2～160.3 ℃, product purity 99.3% (high performance liquid phase area normalization method), and product yield 93.1% is (with 4,4 '-'-biphenyl diphenol meter), the oxirane value actual measurement is 0.668.
Embodiment 7
Ring opening etherification reaction process: with 4; 4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 400 grams, phase-transfer catalyst benzyltriethylammoinium chloride 0.2 gram add in the there-necked flask; logical nitrogen protection; heat up in 80 ℃, reacted 5.0 hours, with high performance liquid chromatography detection reaction raw material 4; 4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 100 ℃, and vacuum tightness increases to and is 0.075Mpa.
Ring-closure reaction process: add 340 gram ethylene dichloride and 13 gram NaOH solids to system then, 80 ℃ the reaction 1 hour after, heating up, ethylene dichloride begins to reflux when 83 spend, tell the water that reaction generates in the system by last minute water water-and-oil separator, react after 10 hours and make 4 with the high performance liquid chromatography detection, 4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction.Carry out the heat washing to system adding tap water and deionized water, remove the inorganic salt in the reaction system and make that organochlorine and inorganic chlorine reach product requirement in the reaction system, the cooling mother liquor is separated out by product, isolate product by filtration or whizzer, oven dry is weighed as 29.6 grams, and melting range is 159.1～160.3 ℃, product purity 99.3% (high performance liquid phase area normalization method), the actual measurement of product yield 93.0% (with 4,4 '-'-biphenyl diphenol meter) oxirane value is 0.650.
Embodiment 8
Ring opening etherification reaction process: with 4; 4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 400 grams, phase-transfer catalyst benzyltriethylammoinium chloride 0.2 gram add and have in the there-necked flask of water trap; logical nitrogen protection; heat up in 80 ℃, reacted 5.0 hours, with high performance liquid chromatography detection reaction raw material 4; 4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 100 ℃, and vacuum tightness is 0.075MPa.
Ring-closure reaction process: add 400 gram toluene and 18.2 gram KOH to system then, 80 ℃ the reaction 1 hour after, heat up and allow refluxing toluene and constantly tell the water that reaction generates in the system with following water-and-oil separator in 110 ℃, react and detect with high performance liquid chromatography after 8 hours, make 4,4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction.Add tap water and deionized water to system and carry out heat and wash, remove inorganic salt, phase-transfer catalyst benzyltriethylammoinium chloride in the reaction system, and make that organochlorine and inorganic chlorine reach product requirement in the reaction system.The cooling mother liquor is separated out by product, filters out product, and oven dry is weighed as 29.5 grams, and melting range is 159.2～160.3 ℃, product purity 99.4% (high performance liquid phase area normalization method), and product yield 93.0% (with 4,4 '-'-biphenyl diphenol meter), the oxirane value actual measurement is 0.656.
Embodiment 9
Ring opening etherification reaction process: with 4; 4 '-'-biphenyl diphenol, 20 grams, epoxy chloropropane 400 grams, phase-transfer catalyst benzyl trimethyl ammonium chloride 0.2 gram add and have in the there-necked flask of water trap; logical nitrogen protection; heat up in 80 ℃, reacted 4.0 hours, with high performance liquid chromatography detection reaction raw material 4; 4 '-'-biphenyl diphenol content is less than 0.5% (mass percent); beginning underpressure distillation epoxy chloropropane, final distillation temperature reaches 100 ℃, and vacuum tightness is 0.075MPa.
Ring-closure reaction process: add 400 gram toluene and 13 gram NaOH to system then, 80 ℃ the reaction 1 hour after, heat up and allow refluxing toluene and constantly tell the water that reaction generates in the system with following water-and-oil separator in 110 ℃, react and detect with high performance liquid chromatography after 8 hours, make 4,4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction.Add tap water and deionized water to system and carry out heat and wash, remove inorganic salt, phase-transfer catalyst benzyl trimethyl ammonium chloride in the reaction system, and make that organochlorine and inorganic chlorine reach product requirement in the reaction system.The cooling mother liquor is separated out by product, filters out product, and oven dry is weighed as 29.8 grams, and melting range is 159.2～160.3 ℃, product purity 99.4% (high performance liquid phase area normalization method), and product yield 93.3% (with 4,4 '-'-biphenyl diphenol meter), the oxirane value actual measurement is 0.653.
Claims (5)
1. one kind 4, the preparation method of 4 '-'-biphenyl diphenol diglycidylether is characterized in that being made up of following steps:
Ring opening etherification reaction process: get 4,4 '-'-biphenyl diphenol, add 4, the epoxy chloropropane that 4 '-'-biphenyl diphenol weight is 16～25 times, add water-soluble stronger phase-transfer catalyst to system then, its add-on is 4,1% of 4 '-'-biphenyl diphenol weight, phase-transfer catalyst is selected from benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, logical nitrogen protection is carried out ring opening etherification reaction at 70～100 ℃, after the reaction needed 3～10 hours, with high performance liquid chromatography detection reaction raw material 4,4 '-'-biphenyl diphenol content is not more than mass percent 0.5%, and the beginning underpressure distillation goes out excessive epoxy chloropropane;
The ring-closure reaction process: in above-mentioned reaction system, add earlier non-polar organic solvent, add-on is 4,17～20 times of 4 '-'-biphenyl diphenol weight; Divide three times again and add the solid alkali powder, solid alkali is selected from solid sodium hydroxide or solid potassium hydroxide, the consumption of solid sodium hydroxide is 4,0.65 times of 4 '-'-biphenyl diphenol compound weight, the add-on of solid potassium hydroxide is 4,0.91 times of 4 '-'-biphenyl diphenol compound weight continues reaction 1 hour down in 80 ℃, heats up, reflux dewatering, and constantly tell in the system water that reaction generates with water-and-oil separator, dehydration reaction detected with high performance liquid chromatography after 5～11 hours, made 4,4-'-biphenyl diphenol 2-glycidyl ether content is greater than 99%, stopped reaction with tap water and deionized water wash mother liquor, washes out the phase-transfer catalyst in the organic system, inorganic salt, the cooling mother liquor is separated out product, filter or the whizzer separation, vacuum-drying promptly gets 4,4 '-'-biphenyl diphenol diglycidylether.
2. according to claim 1 a kind of 4, the preparation method of 4 '-'-biphenyl diphenol diglycidylether is characterized in that: to be selected from atmospheric boiling point be 80～138 ℃ proportion toluene, benzene or the dimethylbenzene lighter than water to non-polar organic solvent in the described ring-closure reaction process.
3. according to claim 2 a kind of 4, the preparation method of 4 '-'-biphenyl diphenol diglycidylether is characterized in that: the proportion of the used non-polar organic solvent of described ring-closure reaction process was lighter than water, with water water-and-oil separator separation in following minute.
4. according to claim 1 a kind of 4, the preparation method of 4 '-'-biphenyl diphenol diglycidylether is characterized in that: non-polar organic solvent is selected from the proportion ethylene dichloride bigger than water in the described ring-closure reaction process.
5. according to claim 4 a kind of 4, the preparation method of 4 '-'-biphenyl diphenol diglycidylether is characterized in that: the proportion of the used non-polar organic solvent of described ring-closure reaction process is bigger than water, uses branch water water-and-oil separator and separates.
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