CN102134314B - Epoxy resin and preparation method thereof - Google Patents

Epoxy resin and preparation method thereof Download PDF

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CN102134314B
CN102134314B CN 201110024360 CN201110024360A CN102134314B CN 102134314 B CN102134314 B CN 102134314B CN 201110024360 CN201110024360 CN 201110024360 CN 201110024360 A CN201110024360 A CN 201110024360A CN 102134314 B CN102134314 B CN 102134314B
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formula
preparation
epoxy
resins
polymkeric substance
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CN102134314A (en
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郑春柏
柳美华
刘宾元
郑晓伟
尹园
邓鹏飏
陈敬强
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Taizhou Feihong Electronics Technology Co ltd
Changchun Institute of Applied Chemistry of CAS
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Taizhou Feihong Electronics Technology Co ltd
Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides an epoxy resin, the structural formula of which is shown in formula I, wherein n equals to 1 to 20, R is a repeating unit shown by formula II, formula III or formula IV, R1 and R2 are respectively methyl or hydrogen; the epoxy resin provided by the invention does not need other blended toughening materials, a functional group with good heat resistance and friction resistance and an epoxide group form the epoxy resin, and the epoxy resin has good toughness. The invention also provides a preparation method of the epoxy resin shown by formula I, which does not need to use a great amount of solvents with a high boiling point, reduces the cost, and avoids inconvenient in aftertreatment caused by use of solvents with a high boiling point.

Description

A kind of Resins, epoxy and preparation method thereof
Technical field
The present invention relates to the polymkeric substance preparation field, relate in particular to a kind of Resins, epoxy and preparation method thereof.
Background technology
Resins, epoxy (EP) is the important thermosetting resin of a class, is widely used matrix resin in the polymer composites.EP has excellent cementability, wear resistance, mechanical property, electrical insulating property, chemical stability and low, the easy machine-shaping of shrinking percentage and the advantage such as with low cost, is used widely in sizing agent, electronic instrument, light industry, building, machinery, space flight and aviation, coating, electric insulating material and prepare composite.But, because pure epoxy resin has higher crosslinking structure, thus have that matter is crisp, the shortcoming such as resistance to fatigue, thermotolerance, toughness are poor, be difficult to satisfy the requirement of engineering, make its application be subject to certain limitation.Therefore be the heat subject of studying both at home and abroad to the toughening modifying of Resins, epoxy always.
Numerous Chinese scholars is devoted to study the toughening modifying method of some new Resins, epoxy in recent years, as with heat-resisting thermoplastic engineering plastic and epoxy blend; Make elastomerics and Resins, epoxy form interpenetrating net polymer (IPN) system; With TLCP to Toughening Epoxy Resin; Epoxy resin toughened etc. with the rigid macromolecule in-situ polymerization.Wherein begin the eighties in 20th century about the research of Toughened With High Performance Thermoplastics Resins, epoxy, use the more resins that thermotolerance is better, mechanical property is high such as polyethersulfone (PES), polysulfones (PSF), polyetherimide (PEI), polyether-ether-ketone (PEEK) that have.These thermoplastic resins not only have preferably toughness, and Young's modulus and thermotolerance are higher, join in the Resins, epoxy as toughner and can form the particle disperse phase, their adding not only makes the toughness of Resins, epoxy be improved, and does not affect modulus and the thermotolerance of curable epoxide resin interpenetrating net polymer.
But, using the method for Toughened With High Performance Thermoplastics all is to reach toughness reinforcing purpose by physical blending or chemical blending method, usage quantity owing to thermoplastic resin in these class methods is generally larger simultaneously, and poorly soluble, need to increase solvability with a large amount of high boiling solvents, such as dimethyl formamide, dimethyl sulfoxide (DMSO) etc., thereby there is certain difficulty in Toughened With High Performance Thermoplastics Resins, epoxy in technique, increased cost.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Resins, epoxy and preparation method thereof, does not come modified epoxy with physics or chemical blend method, has avoided the inconvenience owing to the aftertreatment of using a large amount of high boiling solvents to bring.
The invention provides the Resins, epoxy shown in a kind of formula I,
Figure BDA0000044833580000021
Formula I;
N=1～20 wherein, R is the repeating unit shown in formula II, formula III or the formula IV, R 1, R 2Be respectively methyl or hydrogen;
Figure BDA0000044833580000022
Formula II formula III formula IV.
The present invention also provides the preparation method of the Resins, epoxy shown in a kind of formula I, comprising:
A) with the Resorcinol and 4,4 shown in formula V, formula VI or the formula VII '-difluoro benzophenone, alkali-metal carbonate be blended in the organic solvent, carries out polyreaction, obtains polymkeric substance;
B) polymkeric substance that step a) is obtained and diacetyl oxide, hydrogen peroxide Hybrid Heating, stirring, the initial ring oxidizing reaction obtains the Resins, epoxy shown in the formula I; Wherein R is the repeating unit shown in formula II, formula III or the formula IV, R 1, R 2Be respectively methyl or hydrogen, n=1～20;
Figure BDA0000044833580000023
Formula I;
Figure BDA0000044833580000024
Formula II formula III formula IV
Figure BDA0000044833580000031
Formula V formula VI formula VII.
Preferably, described alkali-metal carbonate is salt of wormwood or yellow soda ash.
Preferably, described polymkeric substance, organic solvent are 1～2: 10～20 by mass volume ratio; Described organic solvent and diacetyl oxide are 1: 1 according to volume ratio.
Preferably, the mass concentration of described hydrogen peroxide is 70%.
Preferably, step a) is specially: a1) under nitrogen protection, be 1～2: 1～2 with the Resorcinol shown in formula V, formula VI or the formula VII and 4,4-difluoro benzophenone, alkali-metal carbonate according to mol ratio: 2～4 are blended in the organic solvent, obtain the first mixing solutions;
A2) described the first mixing solutions is stirred and heated to 100～120 ℃, residuum is heated to 160～180 ℃ after removing the moisture of generation, reaction 1～2h obtains product;
A3) will obtain polymkeric substance after described product filtration, the washing and drying.
Preferably, it is characterized in that described organic solvent is DMF.
Preferably, it is characterized in that described polymkeric substance is the polymkeric substance shown in the formula VIII, wherein n=1～20; Described Y is the repeating unit shown in formula IX～formula XI; R 1, R 2Be respectively methyl or hydrogen;
Figure BDA0000044833580000032
Preferably, when the preparation polymkeric substance, comprise in described organic solvent adding the band aqua.
Preferably, described band aqua is toluene.
The invention provides a kind of Resins, epoxy, shown in I: n=1～20 wherein.R is the repeating unit shown in formula II, formula III or the formula IV, R 1, R 2Be respectively methyl or hydrogen; Resins, epoxy molecular chain provided by the invention is made of the polyaryletherketone repeating unit, has introduced epoxide group and formed Resins, epoxy in polyaryletherketone.Wherein polyaryletherketone has good toughness greatly owing to it is sterically hindered, and wear resisting property is good, good heat resistance, and epoxide group provides high viscosity and less shrinking percentage for whole molecule, can be applied to the multiple industries such as coating, binding agent.
The present invention also provides a kind of preparation method of Resins, epoxy, comprise: the Resorcinol and 4 that will contain bridged ring alkene, 4 '-difluoro benzophenone reflects that in solvent polymerization generates the polyaryletherketone contain the bridge cyclene group, and then react with hydrogen peroxide and diacetyl oxide and the described polyaryletherketone that contains bridged ring alkene, the two keys of alkene disconnect and form an epoxide group, obtain Resins, epoxy, preparation method provided by the invention does not improve the performance of Resins, epoxy with blend, but directly at synthesis phase directly with epoxide group and the combination of polyaryletherketone group, improved the solvability of monomer in solvent, the difficult solvent recovery problem of having avoided using a large amount of high boiling solvents and having caused, improved the processability of Resins, epoxy, with low cost, make the resin of the bright preparation of this law can large-scale industrial production.
Description of drawings
The extension at break rate curve of the Resins, epoxy of Fig. 1 embodiment of the invention 1～7 preparation.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that the just restriction for further specifying the features and advantages of the present invention rather than patent of the present invention being required of these descriptions.
The invention provides a kind of Resins, epoxy, shown in I
Figure BDA0000044833580000041
Formula I;
N=1～20 wherein, R is the repeating unit shown in formula II, formula III or the formula IV, R 1, R 2Be respectively methyl or hydrogen;
Formula II formula III formula IV.
Resins, epoxy provided by the invention is the Resins, epoxy that includes polyaryletherketone, wherein polyaryletherketone has greatly good toughness and intensity owing to it is sterically hindered, wear resisting property is good, good heat resistance, and epoxide group provides high viscosity for whole epoxide resin material and solidify after less shrinking percentage, and, described epoxide group can also react with other functional groups in follow-up reaction as reaction site, or with other crosslinked polymers, thereby improve the performance of Resins, epoxy, and Resins, epoxy provided by the invention is that direct polymerization obtains, when having avoided blending and modifying solubleness low and cause material modified overflow and reduce processibility and physicals.
The present invention also provides a kind of preparation method of Resins, epoxy, comprising: a) with the Resorcinol and 4,4 shown in formula V, formula VI or the formula VII '-difluoro benzophenone, alkali-metal carbonate be blended in the organic solvent, carries out polyreaction, obtains polymkeric substance; B) polymkeric substance that step a) is obtained and diacetyl oxide, hydrogen peroxide Hybrid Heating, stirring oxidation addition obtain the Resins, epoxy shown in the formula I; Wherein R is the repeating unit shown in formula II, formula III or the formula IV, R 1, R 2Be respectively methyl or hydrogen, n=1～20;
Figure BDA0000044833580000052
Formula V formula VI formula VII.
Prepare by the following method according to formula V of the present invention, VI, the described Resorcinol of VIII, the preparation method of the Resorcinol shown in the formula V is:
With cyclopentadiene with contain R 1And/or R 2Para benzoquinone mixed occurrence D-A addition reaction obtain behind the adduct that reduction obtains the Resorcinol shown in the formula V under the effect of aluminium sesquioxide, this Resorcinol also has one two ring [2,2,1]-2-heptene, wherein R 1, R 2Be respectively methyl or hydrogen.
Resorcinol shown in the formula V and cyclopentadiene generation D-A addition reaction are obtained the compound shown in the formula VI.Reaction equation is as follows:
Figure BDA0000044833580000062
The D-A addition reaction is occured with there being substituent para benzoquinone in cyclopentadiene, with the product that obtains at Br 2-CHCl 3The lower reduction of effect obtains the Resorcinol shown in the formula VII.Reaction equation is as follows:
Figure BDA0000044833580000063
According to the present invention, with the Resorcinol and 4 shown in described formula V, VI, the VII, 4 '-the difluoro benzophenone mixing, under the effect of alkaline carbonate, hydrogen on the phenolic hydroxyl group and 4,4 '-hydrogen fluoride on the difluoro benzophenone, the phenolic hydroxyl group that provides a hydrogen becomes ehter bond, with lose 4 of fluorine, 4 '-difluoro benzophenone is the polymkeric substance shown in the formula VIII in conjunction with forming polyaryletherketone, and hydrogen fluoride forms alkali-metal fluorochemical, carbonic acid gas and water with alkali-metal carbonate, makes the pH value of reaction maintain 7～8.Under nitrogen protection, the Resorcinol shown in formula V, formula VI or the formula VII and 4,4-difluoro benzophenone, alkali-metal carbonate are preferably 1～2 according to mol ratio: be blended in organic solvent at 1～2: 2～4, obtains the first mixing solutions according to the present invention; Described the first mixing solutions is stirred and heated to 100～120 ℃, residuum is heated to 160～180 ℃ after removing the moisture of generation, reaction 1～2h obtains product; To obtain polymkeric substance after described product filtration, the washing and drying.Described alkaline carbonate is preferably salt of wormwood or yellow soda ash, described Resorcinol and 4, the mol ratio of 4-difluoro benzophenone, alkali-metal carbonate more preferably 1: 1: 2, described organic solvent is preferably DMF (DMF), and the consumption of described organic solvent is with 4,4-difluoro benzophenone meter, every mole 4, the organic solvent that the 4-difluoro benzophenone uses is preferably 1500mL～2000mL
According to the present invention, the method that the described moisture of removing generation preferably refluxes also preferably adds the band aquas such as toluene, dimethylbenzene in described the first mixed solvent, purpose is in order to make constantly band aqua steam take water vapor out of reaction system in backflow, impel the carrying out of reaction, improved speed of reaction.Usage quantity according to band aqua of the present invention is pressed 4,4-difluoro benzophenone meter, and every mole 4, the 4-difluoro benzophenone uses the band aqua to be preferably 700mL～1000mL,
According to the present invention, described polymkeric substance is the polyaryletherketone shown in the formula VIII, and wherein Y is the repeating unit shown in formula IX, X, the XI.In the polyaryletherketone molecule that the present invention uses bridged ring heptene structure is arranged very, very easily become epoxy compounds by peroxide oxidation and the carbon-to-carbon double bond on the described bridged ring heptene is unstable, obtain Resins, epoxy thereby epoxide group introduced in the polyaryletherketone molecule.
According to the present invention, described polyaryletherketone shown in the formula VIII and hydrogen peroxide and diacetyl oxide are dissolved in the organic solvent, obtain the second mixing solutions.Described organic solvent is preferably N, dinethylformamide, the volume ratio of described organic solvent and diacetyl oxide is for being preferably 1: 1, the mass concentration of described hydrogen peroxide is preferably 70wt%, the mass volume ratio of the polyaryletherketone shown in the described formula VIII and described organic solvent is preferably 1～2: 10～20, more preferably 1～2: 5～8.Described the second mixing solutions is stirred 4～8h under 80～100 ℃, the initial ring oxidizing reaction is cooled to room temperature after reaction finished, and then places frozen water to have floss to separate out described cooled solution, then suction filtration filters out precipitate, obtains leaching thing; The described thing that leaches is carried out vacuum-drying with behind the deionized water wash 2～3 times, be preferably 10～14h time of drying, obtain colourless thick Resins, epoxy.
According to the present invention, be 1～2: 1～2 by the mol ratio of controlling reactant: 2～4, can control polymerization degree n between 1～20, if surpassing this patent scope, mol ratio obtains low polymerization or excessive crosslinked product.Can control polymerization degree n between 100～180 ℃ between 1～20 by the control temperature, temperature is crossed and hanged down then not polymerization reaction take place, and is too high then crosslinked.By the period be 1～2h, can control polymerization degree n between 1～20, the time surpasses the present invention and describes scope and then can produce excessive cross-linking products.
In order to further specify technical scheme of the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described.Need to prove that the source of main raw material used in the present invention and reagent is as follows: cyclopentadiene, 4,4-difluoro benzophenone, bromine water are available from Aladdin reagent.DMF, dimethylbenzene, diacetyl oxide, methylene dichloride are available from the Beijing Chemical Plant.70% hydrogen peroxide is available from Nanchang Suburb nine chemical industry goods and materials company limiteds.
Embodiment 1
Figure BDA0000044833580000081
Formula 1
Resins, epoxy shown in the preparation formula 1 wherein n is 20.
Whipping appts, thermometer, water trap, prolong and N are being housed 2Add the Resorcinol shown in the formula V, wherein R in the reaction flask of gas protector 1, R 2Be hydrogen 17.4g, 0.1mol, 4,4-difluoro benzophenone 21.8g, 0.1mol, salt of wormwood 27.6g, 0.2mol, 150mLDMF and toluene 70mL.Stir, heating, in 120 ℃ with refluxing toluene band water 3.5h after, in water trap, emit the water of toluene and generation, slowly be warming up to 160 ℃, polyreaction 1.5h is poured into water product, suction filtration, with deionized water wash three times, dry 24h obtains polymkeric substance in vacuum drying oven.
Get and make polymkeric substance 10g and be dissolved in and add 50mL diacetyl oxide and 70% hydrogen peroxide behind the 50mL DMF, 80 ℃ of lower 6h that stir pour into after the cooling in the frozen water, suction filtration, deionized water wash final vacuum drying 12h, obtain the colourless thick Resins, epoxy shown in the formula 1 (.
The Resins, epoxy oxirane value that this embodiment obtains is 0.48, and total recovery is that 82%, GPC method records molecular-weight average 5000.Infrared spectra: oxirane ring (3050,1260,920,850cm -1), polyaryletherketone (1654,1592,1498,1157cm -1).
The proton nmr spectra of the Resins, epoxy of present embodiment preparation is: 1HNMR (DMSOppm): 7.70 (2H), 7.66 (2H), 7.36 (2H), 7.02 (2H), 6.69 (1H), 6.47 (1H) 3.17 (2H), 3.02 (2H), 2.09 (2H).
The carbon-13 nmr spectra of the Resins, epoxy of this enforcement preparation is: 13CMR (DMSOppm): 196.3; 160.7; 153.1; 146.3; 139.7; 134; 132.8; 130.3; 130; 128.5; 117.2; 114.1; 125.5; 62.7; 39.7; 36.3,35.
Embodiment 2
Figure BDA0000044833580000091
Formula 2
Resins, epoxy shown in the preparation formula 2, wherein n=2.
Whipping appts, thermometer, water trap, prolong and N are being housed 2Add Resorcinol 25.2g among the formula V, 0.1mol, R in the reaction flask of gas protector 1Be methyl, R 2Be hydrogen, 4,4-difluoro benzophenone 21.8g, 0.1mol, salt of wormwood (27.6g, 0.2mol), 150mLDMF and toluene 70mL.Stir, heating, in 120 ℃ with refluxing toluene band water 3.5h after, in water trap, emit the water of toluene and generation, slowly be warming up to 160 ℃, polyreaction 2h is poured into water product, suction filtration, with deionized water wash three times, dry 24h obtains polymkeric substance in vacuum drying oven.
Get and make the hydrogen peroxide that adds 50mL diacetyl oxide and 70% after polymkeric substance 10g is dissolved among the 50mL DMF, 80 ℃ of lower 6h that stir pour into after the cooling in the frozen water, suction filtration, and deionized water wash final vacuum drying 12h obtains colourless thick Resins, epoxy (1)-b.
The Resins, epoxy oxirane value that this embodiment obtains is 0.52, and total recovery is that 83.2%, GPC method records molecular-weight average 5200.Infrared spectra: oxirane ring (3052,1258,916,830cm -1), polyaryletherketone (1650,1590,1490,1153cm -1)
The proton nmr spectra of the Resins, epoxy of present embodiment preparation is: 1HNMR (DMSOppm): 7.66 (2H), 7.58 (2H), 7.16 (2H), 7.02 (2H), 6.49 (1H), 3.17 (2H), 3.02 (2H), 2.09 (2H), 2.35 (3H).
The carbon-13 nmr spectra of the Resins, epoxy of this enforcement preparation is: 13CMR (DMSOppm): 197.3; 161.7; 150.1; 144.3; 138.7; 132; 130.8; 129.3; 128; 126.5; 117.2; 124.5; 114.1; 62.7; 39.7; 36.3; 35; 15.
Embodiment 3
Figure BDA0000044833580000101
Formula 3
Whipping appts, thermometer, water trap, prolong and N are being housed 2Add the Resorcinol 24.0g shown in the formula V, 0.1mol, wherein R in the reaction flask of gas protector 1, R 2Be methyl, 4,4-difluoro benzophenone 21.8g, 0.1mol, salt of wormwood 27.6g, 0.2mol, 150mLDMF and toluene 70mL.Stir, heating, in 120 ℃ with refluxing toluene band water 3.5h after, in water trap, emit the water of toluene and generation, slowly be warming up to 160 ℃, polyreaction 1.5h is poured into water product, suction filtration, with deionized water wash three times, dry 24h obtains polymkeric substance in vacuum drying oven.
Get and make the hydrogen peroxide that adds 50mL diacetyl oxide and 70% after polymkeric substance 10g is dissolved among the 50mL DMF, 80 ℃ of lower 6h that stir pour into after the cooling in the frozen water, suction filtration, and deionized water wash final vacuum drying 12h obtains colourless thick Resins, epoxy (1)-c.
The Resins, epoxy oxirane value that this embodiment obtains is 0.55, and total recovery is 83.2%.The GPC method records molecular-weight average 5100.Infrared spectra: oxirane ring (3051,1260,925,826cm -1), polyaryletherketone (1652,1600,1489,1150cm -1).
The proton nmr spectra of the Resins, epoxy of present embodiment preparation is: 1HNMR (DMSOppm): 7.70 (2H), 7.66 (2H), 7.36 (2H), 7.02 (2H), 6.49 (1H), 3.17 (2H), 3.02 (2H), 2.09 (2H), 2.35 (6H).
The carbon-13 nmr spectra of the Resins, epoxy of present embodiment preparation is: 13CMR (DMSOppm): 196.3; 160.7; 150; 144.4; 138.7; 132; 130.8; 129.3; 128; 126.5; 117.2; 124.5; 114.1; 62.7; 39.7; 36.3; 35.; 11.9; 8.5.
Embodiment 4
Figure BDA0000044833580000102
Formula 4
Resins, epoxy shown in the preparation formula 4, wherein n=20.
Whipping appts, thermometer, water trap, prolong and N are being housed 2Add the Resorcinol 26.4g shown in the formula VI, 0.1mol, wherein R in the reaction flask of gas protector 1, R 2Be hydrogen, 4,4-difluoro benzophenone 21.8g, 0.1mol, salt of wormwood 27.6g, 0.2mol, 150mLDMF and toluene 70mL.Stir, heating, in 120 ℃ with refluxing toluene band water 3.5h after, in water trap, emit the water of toluene and generation, slowly be warming up to 160 ℃, polyreaction 2.5h is poured into water product, suction filtration, with deionized water wash three times, dry 24h obtains polymkeric substance in vacuum drying oven.
Get and make the hydrogen peroxide that adds 50mL diacetyl oxide and 70% after polymkeric substance 10g is dissolved among the 50mL DMF, 80 ℃ of lower 6h that stir pour into after the cooling in the frozen water, suction filtration, and deionized water wash final vacuum drying 12h obtains faint yellow look thick Resins, epoxy (2)-a.
The Resins, epoxy oxirane value that this embodiment obtains is 0.58, and total recovery is that 85%, GPC method records molecular-weight average 6000.Infrared spectra: oxirane ring (3052,1258,916,830cm -1), polyaryletherketone (1650,1590,1490,1153cm -1).
The proton nmr spectra of the Resins, epoxy of present embodiment preparation is: 1HNMR (DMSOppm): 7.66 (2H), 7.58 (2H), 7.16 (2H), 7.02 (2H), 6.49 (1H), 3.17 (2H), 3.02 (2H), 2.09 (2H), 2.35 (3H).
The carbon-13 nmr spectra of the Resins, epoxy of present embodiment preparation is: 13CMR (DMSOppm): 197.3; 161.7; 150.1; 144.3; 138.7; 132; 130.8; 129.3; 128; 126.5; 117.2; 124.5; 114.1; 62.7; 39.7; 36.3; 35; 15.
Embodiment 5
Figure BDA0000044833580000111
Formula 5
Resins, epoxy shown in the preparation formula 5, wherein n=20.
In the reaction flask that whipping appts, thermometer, water trap, prolong and N2 gas protector are housed, add the Resorcinol 24.0g shown in the formula VI, 0.1mol, wherein R 1Be methyl, R 2Be hydrogen, 4,4-difluoro benzophenone 21.8g, 0.1mol, salt of wormwood 27.6g, 0.2mol, 150mLDMF and toluene 70mL.Stir, heating, in 120 ℃ with refluxing toluene band water 3.5h after, in water trap, emit the water of toluene and generation, slowly be warming up to 160 ℃, polyreaction 1.5h is poured into water product, suction filtration, with deionized water wash three times, dry 24h obtains polymkeric substance in vacuum drying oven.
Get and make the hydrogen peroxide that adds 50mL diacetyl oxide and 70% after polymkeric substance 10g is dissolved among the 50mL DMF, 80 ℃ of lower 6h that stir pour into after the cooling in the frozen water, suction filtration, and deionized water wash final vacuum drying 12h obtains the faint yellow thick Resins, epoxy shown in the formula 5.
The Resins, epoxy oxirane value that this embodiment obtains is 0.54, and total recovery is that 82%, GPC method records molecular-weight average 6200.Infrared spectra: oxirane ring (3052,1280,916,826cm -1), polyaryletherketone (1650,1590,1490,1153cm -1).
The proton nmr spectra of the Resins, epoxy of present embodiment preparation is: 1HNMR (DMSOppm): 7.66 (2H), 7.58 (2H), 7.16 (2H), 7.02 (2H), 6.20 (1H), 3.17 (2H), 3.02 (2H), 2.09 (2H), 2.35 (3H).
The carbon-13 nmr spectra of the Resins, epoxy of present embodiment preparation is: 13CMR (DMSOppm): 196.3; 161.7; 150.1; 144.5; 138.7; 132; 130.8; 129.3; 128; 126.5; 117.2; 124.5; 114.1; 62.7; 39.7; 36.3; 35; 15.
Embodiment 6
Formula 6
Resins, epoxy shown in the preparation formula 6, wherein n=20.
In the reaction flask that whipping appts, thermometer, water trap, prolong and N2 gas protector are housed, add the Resorcinol 24.0g shown in the formula VI, 0.1mol, R 1, R 2Be methyl, Resorcinol, 4,4-difluoro benzophenone 21.8g, 0.1mol, salt of wormwood 27.6g, 0.2mol, 150mLDMF and toluene 70mL.Stir, heating, in 120 ℃ with refluxing toluene band water 3.5h after, in water trap, emit the water of toluene and generation, slowly be warming up to 160 ℃, polyreaction 1.5h is poured into water product, suction filtration, with deionized water wash three times, dry 24h obtains polymkeric substance in vacuum drying oven.
Get and make the hydrogen peroxide that adds 50mL diacetyl oxide and 70% after polymkeric substance 10g is dissolved among the 50mL DMF, 80 ℃ of lower 6h that stir pour into after the cooling in the frozen water, suction filtration, and deionized water wash final vacuum drying 12h obtains suc as formula the faint yellow Resins, epoxy shown in the VI.
The Resins, epoxy oxirane value that this embodiment obtains is 0.53, and total recovery is that 84.5%, GPC method records molecular-weight average 6500.Infrared spectra: oxirane ring (3052,1280,920,830cm -1), polyaryletherketone (1655,1590,1490,1150cm -1).
The proton nmr spectra of the Resins, epoxy of present embodiment preparation is: 1HNMR (DMSOppm): 7.70 (2H), 7.66 (2H), 7.36 (2H), 7.02 (2H), 6.20 (1H), 3.17 (2H), 3.02 (2H), 2.09 (2H), 2.35 (6H).
The carbon-13 nmr spectra of the Resins, epoxy of present embodiment preparation is: 13CMR (DMSOppm): 196.3; 161.7; 150.1; 144.5; 138.7; 132; 130.8; 129.3; 128; 126.5; 117.2; 124.5; 114.1; 62.7; 39.7; 36.3; 35; 11.9; 8.5.
Embodiment 7
Figure BDA0000044833580000131
Formula 7
Resins, epoxy shown in the preparation formula 7, wherein n=20.
In the reaction flask that whipping appts, thermometer, water trap, prolong and N2 gas protector are housed, add the Resorcinol 23.8g shown in the formula VII; 0.1mol, 4; 4-difluoro benzophenone 21.8g, 0.1mol, salt of wormwood 27.6g, 0.2mol, 150mLDMF and toluene 70mL.Stir, heating, in 120 ℃ with refluxing toluene band water 3.5h after, in water trap, emit the water of toluene and generation, slowly be warming up to 160 ℃, polyreaction 1.5h is poured into water product, suction filtration, with deionized water wash three times, dry 24h obtains polymkeric substance in vacuum drying oven.
Get and make the hydrogen peroxide that adds 70mL diacetyl oxide and 70% after polymkeric substance 15g is dissolved among the DMF, 80 ℃ of lower 6h that stir pour into after the cooling in the frozen water, suction filtration, and deionized water wash final vacuum drying 12h obtains the thick Resins, epoxy of brown color.
The Resins, epoxy oxirane value that this embodiment obtains is 0.60, and total recovery is that 80%, GPC method records molecular-weight average 5800.Infrared spectra: oxirane ring (3050,1278,936,824cm -1), polyaryletherketone (1652,1593,1491,1152cm -1).
The proton nmr spectra of the Resins, epoxy of present embodiment preparation is: 1HNMR (DMSOppm): 7.66 (2H), 7.58 (2H), 7.16 (2H), 7.02 (2H), 3.17 (2H), 3.02 (2H), 2.09 (2H).
The carbon-13 nmr spectra of the Resins, epoxy of present embodiment preparation is: 13CMR (DMSOppm): 196.3; 160.7; 145.7; 144.5; 138.7; 132; 130.8; 129.3; 128; 126.5; 117.2; 124.5; 114.1; 62.7; 39.7; 36.6; 35.
Fig. 1 is the elongation at break contrast of the Resins, epoxy of embodiment 1～7 preparation.Wherein origin position is that the elongation at break of the Resins, epoxy of prior art preparation is 2.6%, and the elongation at break of the Resins, epoxy of embodiment 1～7 preparation is all high than the Resins, epoxy for preparing in the prior art, illustrates that Resins, epoxy provided by the invention has better toughness.
Be not difficult to find out from embodiment 1～7, the Resins, epoxy synthesis step of the inventive method preparation is simple, mild condition, need not use catalyzer, the more important thing is the bisphenol A type epoxy resin of comparing traditional blending and modifying, the present invention uses chemosynthesis directly modified group to be introduced in the molecular chain of Resins, epoxy, can not produce material modified owing to solubleness is crossed the low problem such as difficult solvent recovery when using a large amount of high boiling solvents to cause aftertreatment, increase simultaneously toughness, had wider application prospect.
More than to a kind of Resins, epoxy provided by the invention and preparation method thereof.Be described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.

Claims (9)

1. the Resins, epoxy shown in the formula I,
Figure FDA00002409143000011
N=1～20 wherein, R is the repeating unit shown in formula II, formula III or the formula IV, R 1, R 2Be respectively methyl or hydrogen;
Figure FDA00002409143000012
2. the preparation method of the Resins, epoxy shown in the formula I is characterized in that, comprising:
A) with the Resorcinol and 4,4 shown in formula V, formula VI or the formula VII '-difluoro benzophenone, alkali-metal carbonate be blended in the organic solvent, carries out polyreaction, obtains polymkeric substance;
B) polymkeric substance that step a) is obtained and diacetyl oxide, hydrogen peroxide Hybrid Heating, stirring, the initial ring oxidizing reaction obtains the Resins, epoxy shown in the formula I; Wherein R is the repeating unit shown in formula II, formula III or the formula IV, R 1, R 2Be respectively methyl or hydrogen, n=1～20;
Figure FDA00002409143000013
Figure FDA00002409143000021
3. preparation method according to claim 2 is characterized in that, described alkali-metal carbonate is salt of wormwood or yellow soda ash.
4. preparation method according to claim 2 is characterized in that, described polymkeric substance, organic solvent are 1～2:10～20 by mass volume ratio; Described organic solvent and diacetyl oxide are 1:1 according to volume ratio.
5. preparation method according to claim 2, it is characterized in that, step a) is specially: a1) under nitrogen protection, with the Resorcinol and 4 shown in formula V, formula VI or the formula VII, 4-difluoro benzophenone, alkali-metal carbonate are that 1～2:1～2:2～4 are blended in the organic solvent according to mol ratio, obtain the first mixing solutions;
A2) described the first mixing solutions is stirred and heated to 100～120 ℃, residuum is heated to 160～180 ℃ after removing the moisture of generation, reaction 1～2h obtains product;
A3) will obtain polymkeric substance after described product filtration, the washing and drying.
6. any described preparation method is characterized in that according to claim 2～5, and described organic solvent is DMF.
7. any described preparation method is characterized in that according to claim 2～5, and described polymkeric substance is the polymkeric substance shown in the formula VIII, wherein n=1～20; Described Y is the repeating unit shown in formula IX～formula XI; R 1, R 2Be respectively methyl or hydrogen;
Figure FDA00002409143000022
Figure FDA00002409143000031
8. any described preparation method is characterized in that according to claim 2～5, when the preparation polymkeric substance, comprises in described organic solvent adding the band aqua.
9. preparation method according to claim 8 is characterized in that, described band aqua is toluene.
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CN1118788A (en) * 1994-01-26 1996-03-20 布兰科尼尔有机合成研究院 Method to manufacture liquid epoxy resins
CN1670053A (en) * 2004-03-17 2005-09-21 中国科学院化学研究所 Epoxy resin with three functional groups and its derivatives, their preparation method and use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1118788A (en) * 1994-01-26 1996-03-20 布兰科尼尔有机合成研究院 Method to manufacture liquid epoxy resins
CN1670053A (en) * 2004-03-17 2005-09-21 中国科学院化学研究所 Epoxy resin with three functional groups and its derivatives, their preparation method and use

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