CN101962372A - Biphenyl-containing compound liquid crystal epoxy resin and preparation method thereof - Google Patents
Biphenyl-containing compound liquid crystal epoxy resin and preparation method thereof Download PDFInfo
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- CN101962372A CN101962372A CN 201010263036 CN201010263036A CN101962372A CN 101962372 A CN101962372 A CN 101962372A CN 201010263036 CN201010263036 CN 201010263036 CN 201010263036 A CN201010263036 A CN 201010263036A CN 101962372 A CN101962372 A CN 101962372A
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Abstract
The invention provides a biphenyl-containing compound liquid crystal epoxy resin and a preparation method thereof. The biphenyl-containing compound liquid crystal epoxy resin has a structure represented by a formula (1), wherein the -X-Y-, which represents a bridge bond for connecting an aromatic group to a rigid rod mesomorphic structure, may be -C(=O)-O- or-CH=N-; and R1, R2, R3 and R4 and R'1, R'2, R'3 and R'4 has a substituent group which may be -H, -F, -Cl, -Br, -CH3, -C2H5, -OCH3 or -OC2H5. The resin makes full use of the liquid crystal epoxy resin (LCER) thermal performance, and has high comprehensive mechanical performance. The preparation method comprises performing a reaction for generating bisphenol which a liquid crystal epoxy resin intermediate and reacting the bisphenol intermediate with epoxy chloropropane to form the liquid crystal epoxy resin.
Description
Technical field
The present invention relates to a kind of epoxy resin by using liquid crystal (LCER), particularly relate to and contain compound epoxy resin by using liquid crystal of substituent biphenyl and preparation method thereof.
Background technology
Resins, epoxy is a kind of important thermosetting polymer, because that it has an adhesiveproperties is good, and the physical strength height, advantage such as electrical insulating property is good, and cure shrinkage is little is widely used in fields such as machinery, electronics, Aeronautics and Astronautics, chemical industry, communications and transportation, building.But because cured product is the tridimensional network of high crosslink density, the resistance of crack propagation of material and poor toughness, thereby limited its use at some special dimensions.In recent years, utilize the synthetic epoxy compounds that contains just bar-shaped (rigid rod) mesomorphic unit, be epoxy resin by using liquid crystal (LCER), mesomorphic easy generation orientation then forms self-reinforced structure in its solidification process, thereby improve the toughness of cured article, and give performances such as some new machineries of material, heat, photoelectricity, in conjunction with itself intensity height, modulus is big, high temperature resistant and linear expansivity is little characteristics, be expected in performance resins based composites, speciality coating, electronic encapsulating material and nonlinear optical material, be widely used.LCER and matrix material thereof are the products in conjunction with a cross discipline of physics of liquid crystals, organic chemistry, polymer chemistry and Materials science, are approach exploring high performance composite, receive much concern in recent years.
The LCER monomer can be divided into Alpha-Methyl according to the difference of its contained firm Calamitic mesogenic primitive usually
Several mesomorphic structures such as type, aromatic ester type, biphenyl type, methylene amine type and naphthalene type.Novel in recent years LCER is monomeric synthetic and to characterize be one of focus of research both at home and abroad always.Lee et al. points out that performance depends primarily on the length of fragrant mesomorphic group and flexible spacer after the curing of LCER.Mesomorphic phase after the curing is to be controlled by the length-to-diameter ratio of spacer length and mesomorphic group, and in general, just Calamitic mesogenic is long relatively more, the length-to-diameter ratio that is mesomorphic group is high more, and the thermal characteristics that obtains product is good more, the high more (Polymer of thermostability, 2005,45,3677).Cai Zhiqi, grandson build medium people (colleges and universities' chemical industry journal, 23 (3), 2009,510; Journal ofPolymer Science, Part A:Polymer Science:2007,45,727) reported with synthetic 4,4 '-two (the 4-hydroxybenzene methoxyl groups)-3 that obtain of five-step approach, 3 ', 5,5 '-tetramethyl biphenyl diglycidylether, its cured product have higher thermotolerance and keep its liquid crystal liquid crystal property among curing network, but this method yield is very low, and synthetic method is uneconomical.
Summary of the invention
Technical problem to be solved by this invention is, a kind of LCER of making full use of thermal characteristics is provided, the comprehensive mechanical property excellence contain the compound epoxy resin by using liquid crystal of biphenyl.
Another technical problem to be solved of the present invention provides a kind of yield height, raw material is the preparation method who contains the compound epoxy resin by using liquid crystal of biphenyl of convenience goods raw material.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of compound epoxy resin by using liquid crystal of biphenyl that contains has the structure shown in the formula (1):
In the formula ,-X-Y-represents on the rigid rod mesomorphic structure bridged bond that connects aromatic group, for-C (=O)-O-or-CH=N-; Described R
1～R
4And R '
1～R '
4In any substituting group be-H ,-F ,-Cl ,-Br ,-CH
3,-C
2H
5,-OCH
3Or-OC
2H
5
The synthetic method of described epoxy resin by using liquid crystal comprises the steps:
(1) under the nitrogen protection, in high boiling solvent, being raw material with biphenyl compounds and hydroxy phenyl compound, is 100～240 ℃ in temperature, and catalyst action is reaction 2～8h down, directly obtains preparing epoxy resin by using liquid crystal intermediate bis-phenol; Wherein the mol ratio of biphenyl compounds and hydroxy phenyl compound is 1: 4; The mole dosage of high boiling solvent is the 100%-400% of hydroxy phenyl compound; The mole dosage of catalyzer is the 0.1%-3.5% of hydroxy phenyl compound;
Described biphenyl compounds structural formula is:
Y ' is-OH or-NH
2R
1～R
4And R '
1～R '
4In any substituting group be-H ,-F ,-Cl ,-Br ,-CH
3,-C
2H
5,-OCH
3Or-OC
2H
5
Described hydroxy phenyl structural formula of compound is:
X ' is-COOH or-C (=O)-H;
Described high boiling solvent is methyl-sulphoxide, ethylene glycol, glycol ether, Triethylene glycol, tetramethylene sulfone or glycerine;
Described catalyzer is Phenylsulfonic acid, tosic acid, strong phosphoric acid, polyphosphoric acid, the vitriol oil, silicotungstic acid, polystyrolsulfon acid or anhydrous magnesium sulfate;
(2) under the nitrogen protection, being raw material with intermediate bis-phenol and the epoxy chloropropane that obtains in the step (1), is solvent with the Virahol, and under aqueous sodium hydroxide solution catalysis, reaction 2～4h obtains epoxy resin by using liquid crystal; The mol ratio of described intermediate bis-phenol and epoxy chloropropane is 1: 40; The mole dosage of solvent is 20-40 a times of intermediate bis-phenol; The mole dosage of NaOH is 2-8 a times of intermediate bis-phenol.
The weight percent concentration of described aqueous sodium hydroxide solution is preferably 20%～40%.
The present invention first with the convenience goods raw material efficiently synthesized contain formula (1) structure contain the mesomorphic compound firm rod shaped liquid crystal Resins, epoxy of biphenyl type, reaction of the present invention is shown below:
In the formula ,-X-Y-represents on the rigid rod mesomorphic structure bridged bond that connects aromatic group, for-C (=O)-O-or-CH=N-; Described R
1～R
4And R '
1～R '
4In any substituting group be-H ,-F ,-Cl ,-Br ,-CH
3,-C
2H
5,-OCH
3Or-OC
2H
5
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) under not to the situation of protective group, directly obtains preparing epoxy resin by using liquid crystal intermediate bis-phenol, simplified reactions steps, improved the total recovery of reaction by condensation reaction.
(2) be reflected under the nitrogen protection and carry out, prevented of the oxidation of airborne oxygen, improved the visual appearance of product phenolic hydroxyl group.
(3) reaction time range and wider range, the operation that helps reacting.
(4) the reaction conversion ratio height, selectivity is good, by product is few, makes the easy purifying of product, has improved the quality of product.
(5) synthetic method of the present invention is stable, is suitable for the preparation and the production of industrial epoxy resin by using liquid crystal.
Embodiment
The invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
Step 1: two P-hydroxybenzoic acid-3,3 ', 5,5 '-tetramethoxy biphenyl-4,4 '-diester synthetic
Under the nitrogen protection; with P-hydroxybenzoic acid (0.2mol; 27.6g), 3; 3 '; 5,5 '-tetramethoxy biphenyl-4,4 '-diphenol (0.05mol; 15.3g), p-methyl benzenesulfonic acid (3mmol, 0.54g) and tetramethylene sulfone (80ml) joins in the three-necked flask that has stirring rod, water trap and thermometer and stir 6h at 220 ℃.Constantly remove the water that generates in the reaction process.After reaction mixture is cooled to room temperature, be poured in the 500ml water filter cake water that obtains after the filtration and ethanol repetitive scrubbing.Finally obtain being white in color two P-hydroxybenzoic acid-3,3 of powder ', 5,5 '-tetramethoxy biphenyl-4,4 '-diester (23.3g).Productive rate: 85.4%.
Step 2: two (4-(2, the 3-glycidoxy) phenylformic acid)-3,3 ', 5,5 '-tetramethoxy biphenyl-4,4 '-diester synthetic
Under the nitrogen protection, with two P-hydroxybenzoic acid-3,3 ', 5,5 '-tetramethoxy biphenyl-4,4 '-diester (10mmol, 5.5g), epoxy chloropropane (420mmol, 39.2g) and Virahol (320mmol 19.1g) mixes in flask.This mixture is incubated 0.5h down at 50 ℃, and (massfraction 40% 6ml) arrives wherein with 0.15ml/min with aqueous sodium hydroxide solution then.After this continue to stir 3h at 60 ℃.After being cooled to room temperature Deng reaction mixture, be poured in the 500ml water filter cake water that obtains after the filtration and ethanol repetitive scrubbing.Two (4-(2, the 3-glycidoxy) phenylformic acid)-3,3 that finally obtain ', 5,5 '-tetramethoxy biphenyl-4,4 '-diester is white powder (4.95g).Productive rate: 75.1%.
The synthetic method of present embodiment is as follows:
1H-NMR(400MHz，CDCl
3，δ，ppm)：8.11(d，4H，Ar)，7.15(s，4H，Ar)，7.02(d，4H，Ar)，4.23-4.16(m，2H，CH)，3.98-3.94(m，2H，CH)，3.86-3.82(s，12H，CH
3)，2.94(t，2H，CH)，2.70-2.68(m，2H，CH)，2.38(m，2H，CH
2)。
13C-NMR(100MHz，CDCl
3，δ，ppm)：165.1，163.8，149.8，139.4，131.4，130.6，121.3，114.5，107.5，69.5，56.5，51.1，44.6。Using Bruker Avance-400 to carry out nuclear-magnetism characterizes.
1The appearance explanation that is in High-Field 2.94,2.70-2.68,2.38ppm displacement hydrogen among the H-NMR has generated epoxy group(ing).Nuclear-magnetism characterize obtain be target product two (4-(2, the 3-glycidoxy) phenylformic acid)-3,3 ', 5,5 '-tetramethoxy biphenyl-4,4 '-diester.
Embodiment 2
The synthetic method of present embodiment is:
Step 1: two P-hydroxybenzoic acid-3,3 ', 5,5 '-tetramethyl biphenyl-4,4 '-diester synthetic
Under the nitrogen protection; with P-hydroxybenzoic acid (0.2mol; 27.6g), 3; 3 '; 5; 5 '-tetramethyl biphenyl diphenol (0.05mol, 12.1g), p-methyl benzenesulfonic acid (5mmol, 0.9g) and tetramethylene sulfone (50ml) joins in the three-necked flask that has stirring rod, water trap and thermometer and stir 4h at 180 ℃.Constantly remove the water that generates in the reaction process.After reaction mixture is cooled to room temperature, be poured in the 500ml water filter cake water that obtains after the filtration and ethanol repetitive scrubbing.Finally obtain being white in color two P-hydroxybenzoic acid-3,3 of powder ', 5,5 '-tetramethyl biphenyl-4,4 '-diester (19.3g).Productive rate: 80.1%.
Step 2: two (4-(2, the 3-glycidoxy) phenylformic acid)-3,3 ', 5,5 '-tetramethyl biphenyl-4,4 '-diester synthetic
Under the nitrogen protection, with two P-hydroxybenzoic acid-3,3 ', 5,5 '-tetramethyl biphenyl-4,4 '-diester (10.5mmol, 5.1g), epoxy chloropropane (0.42mol, 39.2g) and Virahol (0.32mol 19.1g) mixes in flask.This mixture is incubated 0.5h down at 50 ℃, and (massfraction 30%, 8.5ml) speed with 0.15ml/min is added drop-wise to wherein with aqueous sodium hydroxide solution then.After this continue to stir 4h at 60 ℃.After being cooled to room temperature Deng reaction mixture, be poured in the 500ml water filter cake water that obtains after the filtration and ethanol repetitive scrubbing.Two (4-(2, the 3-glycidoxy) phenylformic acid)-3,3 that finally obtain ', 5,5 '-tetramethyl biphenyl-4,4 '-diester is white powder (4.59g).Productive rate: 73.5%.
1H-NMR(400MHz，CDCl
3，δ，ppm)：8.20(d，4H，Ar)，7.26(s，4H，Ar)，7.02(d，4H，Ar)，4.36-4.33(m，2H，CH)，4.04-4.00(m，2H，CH)，3.40-3.39(m，2H，CH)，2.94(t，2H，CH)，2.80-2.78(m，2H，CH)，2.22(s，12H，CH
3)。
13C-NMR(100MHz，CDCl
3，δ，ppm)：164.1，162.8，147.8，138.4，132.4，130.6，127.4，122.1，114.5，69.0，49.9，44.6，16.6。Using Bruker Avance-400 to carry out nuclear-magnetism characterizes.
1The appearance explanation that is in High-Field 2.94,2.80-2.78ppm displacement hydrogen among the H-NMR has generated epoxy group(ing).Nuclear-magnetism characterize obtain be target product two (4-(2, the 3-glycidoxy) phenylformic acid)-3,3 ', 5,5 '-tetramethyl biphenyl-4,4 '-diester.
Embodiment 3
The synthetic method of present embodiment is:
Fig. 3
Step 1: N, N '-two (4-hydroxy phenyl methylene radical)-2,2 ', 3,3 ', 5,5 ', 6,6 '-octafluoro biphenyl-4,4 '-diamines synthetic
Under the nitrogen protection, with p-Hydroxybenzaldehyde (0.2mol, 24.4g), 2,2 '; 3,3 ', 5,5 '; 6,6 '-octafluoro biphenyl-4,4 '-diamines (0.05mol, 16.4g) and methyl-sulphoxide (40ml) joins in the three-necked flask that has stirring rod and thermometer and stir 3h at 100 ℃.After reaction mixture is cooled to room temperature, be poured in the 500ml water filter cake water that obtains after the filtration and ethanol repetitive scrubbing.Finally obtain the N of pinkiness powder, N '-two (4-hydroxy phenyl methylene radical)-2,2 ', 3,3 ', 5,5 ', 6,6 '-octafluoro biphenyl-4,4 '-diamines (25.5g).Productive rate: 95.2%.
Step 2: N, N '-two (4-(2, the 3-glycidoxy)-phenylmethylene)-2,2 ', 3,3 ', 5,5 ', 6,6 '-octafluoro biphenyl-4,4 '-diamines synthetic
Under the nitrogen protection, with N, N '-two (4-hydroxy phenyl methylene radical)-2,2 ', 3; 3 ', 5,5 ', 6,6 '-octafluoro biphenyl-4; 4 '-diamines (10mmol, 5.4g), epoxy chloropropane (0.42mol, 39.2g) and Virahol (0.32mol 19.1g) mixes in flask.This mixture is incubated 0.5h down at 50 ℃, and (massfraction 20%, 10ml) speed with 0.15ml/min is added drop-wise to wherein with aqueous sodium hydroxide solution then.After this continue to stir 2h at 60 ℃.After being cooled to room temperature Deng reaction mixture, be poured in the 500ml water filter cake water that obtains after the filtration and ethanol repetitive scrubbing.The N that finally obtains, N '-two (4-(2, the 3-glycidoxy)-phenylmethylene)-2,2 ', 3,3 ', 5,5 ', 6,6 '-octafluoro biphenyl-4,4 '-diamines is pink powder (4.94g).Productive rate: 76.2%.
1H-NMR(400MHz，CDCl
3，δ，ppm)：8.41(s，2H，N＝C-H)，7.85(d，4H，Ar)，7.06(d，4H，Ar)，4.23-4.16(m，2H，CH)，3.97-3.94(m，2H，CH)，3.06-3.02(m，2H，CH)，2.70-2.68(m，2H，CH)，2.38(m，2H，CH
2)。
13C-NMR(100MHz，CDCl
3，δ，ppm)：162.1，160.8，145.3，139.9，129.8，129.3，128.2，120.1，114.5，69.5，52.1，44.4。Using Bruker Avance-400 to carry out nuclear-magnetism characterizes.
1The appearance explanation that is in High-Field 3.06-3.02,2.70-2.68,2.38ppm displacement hydrogen among the H-NMR has generated epoxy group(ing).That the nuclear-magnetism sign obtains is target product N, N '-two (4-(2, the 3-glycidoxy)-phenylmethylene)-2,2 ', 3,3 ', 5,5 ', 6,6 '-octafluoro biphenyl-4,4 '-diamines.
To the epoxy resin by using liquid crystal of above three embodiment preparation respectively with solidifying agent 4,4 '-mould of packing into after diaminodiphenylmethane metering mixes pours into a mould, and the cast thing is at 70 ℃ of insulation 2h, at 150 ℃ of insulation 4h, be processed to form cured article cross-linked network matrix material under the temperature program(me) of 180 ℃ of insulation 2h.Composite sample carries out test performance, and it the results are shown in Table 1.Wherein, mould is made according to GB/T2567-2008.The epoxy equivalent (weight) of used Resins, epoxy E-51 between (0.48～0.54)/100 grams, organic chlorine number between between the gram of (0～0.02)/100, inorganic chlorine number between between the gram of (0～0.001)/100, viscosity is not more than 2.5PaS (35 ℃), volatile content is not higher than 1.5%.Use SunS electronic type universal trier according to GB/T2567-2008 test tensile strength, elongation at break and flexural strength.Use XJC-11D polarity formula combination shock-testing machine to measure breach and unnotched shock strength according to GB/T2567-2008.Use the dynamic thermomechanical property of Netzsch DMA242 measure sample.Use Netzsch STA 449C test resistance toheat.
Can be seen that by table 1 the sample tensile strength of the resulting epoxy resin by using liquid crystal of the present invention, flexural strength be all than E-51 system height, shock strength improves especially obvious, has improved significantly that the ordinary epoxy resin material fragility is big, the shortcoming of poor toughness.The epoxy resin by using liquid crystal matrix material that the present invention obtains just has the storage modulus much higher than E-51 at vitreous state, for other method for toughening, as the toughness reinforcing ordinary epoxy resin of rubber elastomer is cost to sacrifice Young's modulus but, and the toughness reinforcing ordinary epoxy resin of epoxy resin by using liquid crystal has remarkable advantages.Initial weightless temperature of epoxy resin by using liquid crystal matrix material that the present invention simultaneously obtains and 600 ℃ remaining quality all increase than the E-51 system, have also improved thermotolerance when improving Resins, epoxy intensity, have excellent heat resisting.The resulting epoxy resin by using liquid crystal of the present invention can not only improve the toughness of Resins, epoxy significantly, and can also improve the intensity and the thermotolerance of Resins, epoxy, be to be used for Resins, epoxy from now on to strengthen one of toughness reinforcing most promising method, can be widely used in Resins, epoxy and strengthen toughness reinforcing field.
Table 1
Claims (3)
1. one kind contains the compound epoxy resin by using liquid crystal of biphenyl, it is characterized in that it has the structure shown in the formula (1):
In the formula ,-X-Y-represents on the rigid rod mesomorphic structure bridged bond that connects aromatic group, for-C (=O)-O-or-CH=N-; Described R
1～R
4And R '
1～R '
4In any substituting group be-H ,-F ,-Cl ,-Br ,-CH
3,-C
2H
5,-OCH
3Or-OC
2H
5
2. the synthetic method of the described epoxy resin by using liquid crystal of claim 1 is characterized in that comprising the steps:
(1) under the nitrogen protection, in high boiling solvent, being raw material with biphenyl compounds and hydroxy phenyl compound, is 100～240 ℃ in temperature, and catalyst action is reaction 2～8h down, directly obtains preparing epoxy resin by using liquid crystal intermediate bis-phenol; Wherein the mol ratio of biphenyl compounds and hydroxy phenyl compound is 1: 4; The mole dosage of high boiling solvent is the 100%-400% of hydroxy phenyl compound; The mole dosage of catalyzer is the 0.1%-3.5% of hydroxy phenyl compound;
Described biphenyl compounds structural formula is:
Y ' is-OH or-NH
2R
1～R
4And R '
1～R '
4In any substituting group be-H ,-F ,-Cl ,-Br ,-CH
3,-C
2H
5,-OCH
3Or-OC
2H
5
Described hydroxy phenyl structural formula of compound is:
X ' is-COOH or-C (=O)-H;
Described high boiling solvent is methyl-sulphoxide, ethylene glycol, glycol ether, Triethylene glycol, tetramethylene sulfone or glycerine;
Described catalyzer is Phenylsulfonic acid, tosic acid, strong phosphoric acid, polyphosphoric acid, the vitriol oil, silicotungstic acid, polystyrolsulfon acid or anhydrous magnesium sulfate;
(2) under the nitrogen protection, being raw material with intermediate bis-phenol and the epoxy chloropropane that obtains in the step (1), is solvent with the Virahol, and under aqueous sodium hydroxide solution catalysis, reaction 2～4h obtains epoxy resin by using liquid crystal; The mol ratio of described intermediate bis-phenol and epoxy chloropropane is 1: 40; The mole dosage of solvent is 20-40 a times of intermediate bis-phenol; The mole dosage of NaOH is 2-8 a times of intermediate bis-phenol.
3. the synthetic method of epoxy resin by using liquid crystal according to claim 2, it is characterized in that: the weight percent concentration of described aqueous sodium hydroxide solution is 20%～40%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408510A (en) * | 2013-07-26 | 2013-11-27 | 深圳先进技术研究院 | Epoxy resin compound of liquid crystal containing naphthalene, and preparation method and composition thereof |
| CN104530387A (en) * | 2014-12-18 | 2015-04-22 | 中科院广州化学有限公司 | Liquid crystal epoxy resin as well as preparation method and application thereof |
| CN108484534A (en) * | 2018-04-24 | 2018-09-04 | 深圳华力兴新材料股份有限公司 | A kind of epoxy type chain extender and preparation method thereof |
| CN114163776A (en) * | 2022-01-24 | 2022-03-11 | 西南石油大学 | Epoxy resin with pressure-bearing and leakage-stopping functions and preparation method thereof |
| CN117304036A (en) * | 2023-09-20 | 2023-12-29 | 奥盖尼克材料(苏州)有限公司 | Preparation method of octafluoro- [1,1 '-biphenyl ] -4,4' -diamine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958719A (en) * | 2006-11-30 | 2007-05-09 | 复旦大学 | Schiff's base type epoxy resin of liquid crystal, preparation method and application |
-
2010
- 2010-08-24 CN CN 201010263036 patent/CN101962372A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958719A (en) * | 2006-11-30 | 2007-05-09 | 复旦大学 | Schiff's base type epoxy resin of liquid crystal, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 《Polym. Bull.》 20100811 Yin-Ling Liu et.al A new and efficient synthetic method of a liquid crystalline epoxy resin with biphenol and aromatic ester group 57-66 第67卷, 第1期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408510A (en) * | 2013-07-26 | 2013-11-27 | 深圳先进技术研究院 | Epoxy resin compound of liquid crystal containing naphthalene, and preparation method and composition thereof |
| CN103408510B (en) * | 2013-07-26 | 2015-12-09 | 深圳先进技术研究院 | Containing naphthalene epoxy resin by using liquid crystal compound, its preparation method and composition |
| CN104530387A (en) * | 2014-12-18 | 2015-04-22 | 中科院广州化学有限公司 | Liquid crystal epoxy resin as well as preparation method and application thereof |
| CN108484534A (en) * | 2018-04-24 | 2018-09-04 | 深圳华力兴新材料股份有限公司 | A kind of epoxy type chain extender and preparation method thereof |
| CN114163776A (en) * | 2022-01-24 | 2022-03-11 | 西南石油大学 | Epoxy resin with pressure-bearing and leakage-stopping functions and preparation method thereof |
| CN117304036A (en) * | 2023-09-20 | 2023-12-29 | 奥盖尼克材料(苏州)有限公司 | Preparation method of octafluoro- [1,1 '-biphenyl ] -4,4' -diamine |
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Application publication date: 20110202 |