CN1631930A - Liquid crystal epoxy resin with branched chain, its preparing method, composition and use - Google Patents
Liquid crystal epoxy resin with branched chain, its preparing method, composition and use Download PDFInfo
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- CN1631930A CN1631930A CN 200410052408 CN200410052408A CN1631930A CN 1631930 A CN1631930 A CN 1631930A CN 200410052408 CN200410052408 CN 200410052408 CN 200410052408 A CN200410052408 A CN 200410052408A CN 1631930 A CN1631930 A CN 1631930A
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Abstract
The invention relates to liquid crystal epoxide resin wit branch chain, its (1) is shown at the right: R is alkyl containing 1-16 carbon atom, m=1-10, also it relates to the method to prepare the compound, the combination and its application. The invention has the characteristic that the product etherealized and then esterified of methyl p-hydroxybenzoate and alkenyl alkyl halide has reaction with the product of 2,5-dihydroxy-benzoic acid and alkyl alcohol or alkyl halide, the compound generated then reacts with peroxiding agent, making the liquid crystal epoxide resin with branch chain, and the productivity is as high as 70-85%, much higher than the conventional dirct esterification method. The invention has the performance of liquid crystal, and lower melt point than that without branch chain, can be solified by many curing agent in lower temperature for producing electronic enclosing material and shape-mambering material with outstanding performance.
Description
Technical field
The present invention relates to epoxy resin by using liquid crystal of a kind of novelty and preparation method thereof, and the composition and use thereof of this Resins, epoxy, especially relate to a kind of branched epoxy resin by using liquid crystal and preparation method thereof, composition and purposes.
Background technology
Liquid crystal polymer is a kind of polymer that exists with liquid crystal state under given conditions, compare with general polymer, it has distinctive molecular orientation of mesomorphic phase and location orientation, compares with the small molecules liquid crystalline cpd, and it has the characteristic of high molecule mass and macromolecular compound again.The physicals that liquid crystal polymer can not be compared because of its excellent mechanical property or other materials obtains the common concern and the attention of academia and industry member.
According to the formation condition of liquid crystal, liquid crystal polymer is divided into thermotropic and the molten type that causes.The thermoset liquid crystal polymer is the another class novel liquid crystal macromolecular material that grows up on the thermotropic liquid crystalline polymer basis, it has the characteristics of small molecules liquid crystal and liquid crystal polymer concurrently, uncured crosslinked preceding liquid crystal state viscosity is low, easily processing, organizer form height molecule behind the curing cross-linked, overcome the shortcoming of thermotropic liquid crystalline polymer at the vertical direction intensity difference of orientation, so thermoset liquid crystal polymer notion is once proposition, just receive much attention, particularly the thermoset liquid crystal high polymer material becomes the research focus over past ten years.
Because the crosslinking reaction mechanism of the epoxide group of epoxy resin by using liquid crystal and solidifying agent is clear and definite, reaction is control easily, and can be by the synthetic polymeric system of the structure that changes epoxy compounds and solidifying agent with different performance, satisfying the different application requirement, thereby epoxy resin by using liquid crystal is the research focus of thermoset liquid crystal polymer.
In research in the past, it is found that, the curing reaction of epoxy resin by using liquid crystal is if carry out under the mesomorphic phase temperature, spontaneous or the outer field orientation orientation in edge of mesomorphic unit this moment, system degree of order height, can make by curing reaction and thisly irreversibly to be fixed up in order, promptly ordered structure " is freezed " in network; If curing reaction carries out under isotropic temperature, the mesomorphic unit lack of alignment mainly forms amorphous network; Generally there are the various physicalies of sequence network will be higher than the performance of no sequence network.So in order to obtain high performance liquid crystalline epoxy cured article, epoxy resin by using liquid crystal solidifies and should carry out in the low-temperature end of mesomorphic phase temperature range.But in the liquid crystalline epoxy monomer molecule structure inflexible mesomorphic unit is arranged, the molecule symmetry, so most liquid crystalline epoxy monomer fusing points are higher, even the low-temperature end in the mesomorphic phase temperature is solidified, because of the temperature of reaction height, curing reaction is very fast, molecular chain has little time abundant adjustment, both be unfavorable for being formed with the high liquid crystalline epoxy cured article of preface degree, and also made curing reaction restive, caused producing in the liquid crystalline epoxy cured article defectives such as pore.This also is the less major cause of relevant epoxy resin by using liquid crystal material macro-mechanical property (as intensity, modulus etc.) report in the present document.Therefore,, must reduce the monomeric fusing point of liquid crystalline epoxy effectively, thereby make curing reaction can under lower temperature, carry out (as being lower than 150 ℃) in order to obtain the epoxy resin by using liquid crystal of high performance easy machine-shaping.
Summary of the invention
The object of the present invention is to provide the epoxy resin by using liquid crystal that a kind of fusing point is low, process window is wide, another purpose is to provide the preparation method of this epoxy resin by using liquid crystal high yield, another purpose is to provide the composition of this epoxy resin by using liquid crystal and solidifying agent, and another purpose is to provide the purposes of this composition.
The present invention is under the effect of catalyzer; make product and the branched Resorcinol generation nucleophilic reaction of carboxylic acid through acidylate; epoxidation again; can high yield obtain low-melting branched epoxy resin by using liquid crystal; this epoxy resin by using liquid crystal can obtain the electronic package material and the shape-memory material of various performances by a variety of solidifying agent curing at a lower temperature, thereby has realized purpose of the present invention.
Branched epoxy resin by using liquid crystal of the present invention, feature are that its structure is represented by general formula (1):
Formula (1)
Wherein R represents to contain the alkyl of 1～16 carbon atom, m=1～10.
The preparation method of branched epoxy resin by using liquid crystal of the present invention, feature are that its step comprises:
(1) compound of difference preparation formula (2) and formula (3): 2, the 5-resorcylic acid reacts with alkyl alcohol that contains 1～16 carbon atom or halogenated alkane, obtains the compound of formula (2); Methyl p-hydroxybenzoate and the functional group of containing 3～12 carbon atoms lay respectively at the chloro-alkenes at chain two ends or bromo alkene at catalyzer, under the condition that alkaline condition and solvent exist, obtain the compound of formula (3):
Formula (2) formula (3)
(2) compound of formula (3) under 70～100 ℃ by the acylating agent acidylate after, the compound of acylate that obtains and formula (2) is at catalyst n, under the effect of N-dimethyl aminopyridine, in basic solvent-20～20 ℃ down reaction obtain the compounds of formula (4):
Formula (4)
R in formula (2), (3) and (4) compound and m cotype (1) compound;
(3) compound of formula (4) reacts with the peroxidation agent in organic solvent, and temperature is controlled at 20～60 ℃, obtains branched epoxy resin by using liquid crystal, i.e. the compound of general formula (1).
Among the preparation method of branched epoxy resin by using liquid crystal of the present invention, the epoxidation reaction of the compound of the preparation of formula (2) and formula (3) compound, the acidylate of formula (3) compound and formula (4) all is conventional reaction method.
Among the preparation method of branched epoxy resin by using liquid crystal of the present invention, in mole number, in the described step (1) preferably 1 part 2,5-resorcylic acid and 1～5 part of alkyl alcohol or halogenated alkane reaction, 1 part of methyl p-hydroxybenzoate and 1～5 part of described chloro-alkenes or bromo olefine reaction; The preferably compound of 2 parts of formulas (3) and 2～10 parts of acylation reactions in the described step (2), the compound reaction of 2～5 parts of acylates and 1 part of formula (2); The preferably compound of 1 part of formula (4) and 1～6 part of peroxidation agent reaction in the described step (3).
Among the preparation method of branched epoxy resin by using liquid crystal of the present invention, in the step (1) during the compound of preparation formula (2) described alkyl alcohol can be propyl carbinol, n-hexyl alcohol, n-Octanol, 1-tridecanol, isooctyl alcohol, 2-tridecanol etc., described halogenated alkane can be the 1-n-butyl bromide, hexyl bromide 1 bromohexane, 1-bromooctane etc., described reaction has needs catalyzer, having does not need catalyzer, catalyst system therefor generally is the vitriol oil, tosic acid etc., temperature of reaction is 25～150 ℃, reaction times is 2～15 hours, chloro-alkenes or bromo alkene that functional group described in during the compound of preparation formula (3) lays respectively at the chain two ends can be chlorallylenes, allyl bromide 98,4-bromo-1-butylene, 6-bromo-1-hexene etc., described catalyzer is crown ether-like material such as 18-hat-6-ether preferably, 15-hat-5-ether, dibenzo-18-hat-6-ether etc., the usage quantity of described catalyzer is in preferably 0.005～0.5 part of mole number, described alkali is sodium hydroxide, yellow soda ash, sodium bicarbonate, potassium hydroxide, salt of wormwood, saleratus etc., described solvent is deionized water preferably, acetone, pyridine, triethylamine, picoline etc., temperature of reaction is 40～90 ℃, preferably 2～48 hours reaction times; Acylating agent described in the step (2) is thionyl chloride preferably, phosphorus trichloride, phosphorus pentachloride etc., the usage quantity of described catalyzer is in preferably 0.001～0.5 part of mole number, described basic solvent is pyridine preferably, triethylamine, picoline etc., and the reaction times is 2～48 hours; Peroxidation agent described in the step (3) is peroxidation 0-chloro-benzoic acid etc. preferably, and described organic solvent is ether, chloroform, ethylene dichloride, acetone, benzene etc. preferably, and the reaction times is 4～200 hours.
The composition of the branched epoxy resin by using liquid crystal of the present invention is characterized in that by mole number, is made up of compound and 0.5～1.2 part of solidifying agent of 1 part of general formula (1).
Described solidifying agent is aromatic amine such as diaminodiphenyl-methane, diamino diphenyl sulfone, mphenylenediamine etc. preferably, acid anhydrides such as phthalic anhydride, methyl tetrahydrophthalic anhydride, benzophenone tetracarboxylic dianhydride etc., resol, polythiol, isocyanic ester etc., aliphatic amide such as quadrol, two (4-aminocyclohexyl) methane, polymeric amide-polyamines etc.
Composition of the present invention is used for electronic package material and shape-memory material.
For example, 1 part of side chain contains 1～6 carbon atom among the present invention epoxy resin by using liquid crystal and 0.5～1.2 part of solidifying agent mix, 50～140 ℃ of Procuring 1～36 hour, then 120～180 ℃ of after fixing 0.5～10 hour, can be used to prepare electronic package material, wherein solidifying agent can be aromatic amine (diaminodiphenyl-methane, diamino diphenyl sulfone, a mphenylenediamine etc.), acid anhydrides (phthalic anhydride, methyl tetrahydrophthalic anhydride, benzophenone tetracarboxylic dianhydride etc.), resol, polythiol, a kind of in the isocyanic ester etc.The specific inductivity of this encapsulating compound can reach 2.1 (60Hz, ASTM D150), and second-order transition temperature reaches 160 ℃.
And for example, 1 part of side chain contains the epoxy resin by using liquid crystal of 3～16 carbon atoms and mixing of 0.5～1.2 part of solidifying agent among the present invention, 20～140 ℃ of Procuring 1～36 hour, then 120～180 ℃ of after fixing 0.5～10 hour, can be used to prepare shape-memory material, wherein solidifying agent can be a kind of in aliphatic amide (quadrol, two (4-aminocyclohexyl) methane, polymeric amide-polyamines etc.), the aromatic amine (diaminodiphenyl-methane, diamino diphenyl sulfone, mphenylenediamine etc.) etc.This material deformation amount is below 20%, and the shape memory recovery temperature reaches 90～160 ℃.
The present invention has been compared with the prior art following advantage.
Branched epoxy resin by using liquid crystal of the present invention is with the same liquid crystal property that all has of not branched epoxy resin by using liquid crystal, and is still low than not branched epoxy resin by using liquid crystal fusing point.Preparation method of the present invention adopts first acidylate, carries out nucleophilic reaction again under catalyzer, and the productive rate that therefore obtains epoxy resin by using liquid crystal can reach 70～85%, greatly improves than traditional direct esterification method.
The fusing point of branched epoxy resin by using liquid crystal of the present invention is low, the curing reaction of itself and solidifying agent therefore easy to control, avoid the hot setting defective, therefore the specific inductivity of the electronic package material that makes can reach 2.1 (60Hz, ASTM D150), second-order transition temperature reaches 160 ℃, and the shape-memory material that makes has deformation quantity low (below 20%), shape memory recovery temperature height common shape such as (90～160 ℃) is remembered the advantage that polymer does not possess.
Embodiment
Following embodiment further specifies of the present invention, is not limitation of the present invention.
Embodiment 1:
With the 0.01mol chlorallylene, 0.01mol methyl p-hydroxybenzoate, 1g18-hat-6-ether and 10g salt of wormwood add in the 100mL acetone, and 50 ℃ were reacted 20 hours down, obtain para Toluic Acid's allyl ethers.0.01mol 2,5-resorcylic acid and 0.01mol n-Octanol 80 ℃ of reactions 7 hours, use the 1000mL solvent extraction under the effect of the 6mL vitriol oil, the volume ratio of second alcohol and water is 3: 1 in the solvent, must 2,5-resorcylic acid n-octyl.0.01mol para Toluic Acid's allyl ethers and 20mL thionyl chloride are 90 ℃ of following acidylates, 2 of acylate that obtains and 0.01mol, 5-resorcylic acid n-octyl are at 0.4gN, and under the effect of N-dimethyl aminopyridine, 0 ℃ of reaction obtains m=1, R=C
8H
17The compound of formula (4).0.01mol this compound is a solvent with the 100mL methylene dichloride, through 45 ℃ of reactions of the adjacent chloro peroxide acid of 0.03mol 120 hours, the product that obtains was through nucleus magnetic resonance, and confirmation is R=C
8H
17, the formula of m=1 (1) band side chain epoxy resin by using liquid crystal.The DSC data are as follows: fusing point is 76 ℃, and clearing point is 86 ℃.
The data of nucleus magnetic resonance are as follows:
1HNMR.[CDCl3/TMS, δ (ppm)]: 0.84 (3H, t, CH
3), 1.23 (10H, m, CH
2), 1.46 (2H, m, CH
2), 2.78 (2H, m, the CH of epoxy
2), 2.93 (2H, dd, the CH of epoxy
2), 3.38 (2H, t, the CH of epoxy), 4.01 (2H, m ,-O-CH
2), 4.12 (2H, t ,-CH
2-OOC-), 4.32 (2H, m ,-O-CH
2), 7.00 (4H, dd, aromatic), 7.23 (1H, s, aromatic), 7.43 (1H, d, aromatic), 7.87 (1H, s, aromatic), 8.15 (4H, dd, aromati).
Embodiment 2:
With 0.01mol4-chloro-1-butylene, the 0.01mol methyl p-hydroxybenzoate, 1.5g dibenzo-18-hat-6-ether, 10g salt of wormwood adding 150mL reacted 20 hours down at 65 ℃ in the acetone, obtained para Toluic Acid's alkene butyl ether.0.01mol 2, the positive tetradecyl alcohol of 5-resorcylic acid and 0.01mol 120 ℃ of reactions 6 hours, use the 1000mL solvent extraction under the effect of tosic acid, the volume ratio of second alcohol and water is 5: 1 in the solvent, must 2, positive 14 esters of 5-resorcylic acid.0.01mol para Toluic Acid's alkene butyl ether in thionyl chloride 90 ℃ of following acidylates; 2 of acylate that obtains and 0.01mol mole, positive 14 esters of 5-resorcylic acid are at 1g N, under the effect of N-dimethyl aminopyridine;-5 ℃ of reactions obtained m=2, R=C in 16 hours
14H
29The compound of formula (4).0.01mol this compound is a solvent with the 100ml methylene dichloride, through 40 ℃ of reactions of the adjacent chloro peroxide acid of 0.03mol 150 hours, the product that obtains turned out to be R=C through nucleus magnetic resonance
14H
29, the formula of m=2 (1) band side chain epoxy resin by using liquid crystal.The DSC data are as follows: its fusing point is 54 ℃, and clearing point is 69 ℃.
The data of nucleus magnetic resonance are as follows:
1HNMR.[CDCl3/TMS, δ (ppm)]: 0.83 (3H, t, CH
3), 1.21 (22H, m, CH
2), 1.43 (2H, m, CH
2), 2.77 (2H, m, the CH of epoxy
2), 2.93 (2H, dd, the CH of epoxy
2), 3.38 (2H, t, the CH of epoxy), 4.02 (2H, m ,-O-CH
2), 4.14 (2H, t ,-CH
2-OOC-), 4.32 (2H, m ,-O-CH
2), 7.01 (4H, dd, aromatic), 7.23 (1H, s, aromatic), 7.43 (1H, d, aromatic), 7.87 (1H, s, aromatic), 8.16 (4H, dd, aromati).
Embodiment 3:
With the 0.01mol chlorallylene, the 0.01mol methyl p-hydroxybenzoate, 0.7g 15-hat-5-ether 6g sodium hydroxide adds the 100mL deionized water, reacts 20 hours down at 50 ℃, obtains para Toluic Acid's allyl ethers.0.01mol 2,5-resorcylic acid and 0.01mol1-bromine normal butane in the 100mL triethylamine 30 ℃ the reaction 6 hours, use the 1000mL solvent washing, solvent is 5% sodium bicarbonate aqueous solution, vacuum-drying then obtains 2, the positive butyl ester of 5-resorcylic acid.0.01mol para Toluic Acid's allyl ethers and 20ml thionyl chloride are 85 ℃ of following acidylates; 2 of the acylate that obtains and 0.01 mole, the positive butyl ester of 5-resorcylic acid is at the 1g catalyst n, under the effect of N-dimethyl aminopyridine;-5 ℃ of reactions obtained m=1, R=C in 20 hours
4H
9The compound of formula (4).0.01mol this compound is a solvent with the 100mL methylene dichloride, with 50 ℃ of reactions of the adjacent chloro peroxide acid of 0.03mol 36 hours, the product that obtains turned out to be m=1 through nucleus magnetic resonance, R=C
4H
9Formula (1) band side chain epoxy resin by using liquid crystal.The DSC data are as follows: its fusing point is 96 ℃, and clearing point is 118 ℃.
The data of nucleus magnetic resonance are as follows:
1HNMR.[CDCl3/TMS, δ (ppm)]: 0.85 (3H, t, CH
3), 1.25 (4H, m, CH
2), 1.45 (2H, m, CH
2), 2.78 (2H, m, the CH of epoxy
2), 2.93 (2H, dd, the CH of epoxy
2), 3.38 (2H, t, the CH of epoxy), 4.01 (2H, m ,-O-CH
2), 4.08 (2H, t ,-CH
2-OOC-), 4.32 (2H, m ,-O-CH
2), 7.00 (4H, dd, aromatic), 7.23 (1H, s, aromatic), 7.43 (1H, d, aromatic), 7.87 (1H, s, aromatic), 8.16 (4H, dd, aromati).
Embodiment 4:
Milling under the epoxy resin by using liquid crystal that the embodiment 3 of 0.02mol is obtained and the 0.01 mole of para diaminobenzene base sulfoxide room temperature mixes, and is heated to 160 ℃ of stirrings, then cooling rapidly.This mixture solidified 3 hours down at 100 ℃, and then 140 ℃ of reactions 1 hour, 180 ℃ were reacted 1 hour, and the degradation temperature of the composition that obtains is 310 ℃, and at 60Hz, 230 ℃ of following specific inductivity are 2.13.
Embodiment 5:
Epoxy resin by using liquid crystal and 0.01 mole of diaminodiphenyl-methane that 0.02 mole embodiment 1 is obtained are solvent with the 20mL trichloromethane, mix, solvent evaporates is fallen in the room temperature decompression, this mixture solidified 6 hours down at 65 ℃, 120 ℃ of reactions 1 hour, 150 ℃ were reacted the straight bar-shaped cured product that obtains 1 hour then, be cooled to room temperature after 150 ℃ of bendings more rapidly, product still keeps curved shape.After being warmed up to 150 ℃ again, directly bar-shaped when this product recovers to solidify rapidly.
Claims (7)
1. the compound of following general formula (1):
Formula (1)
Wherein R represents to contain the alkyl of 1～16 carbon atom, m=1～10.
2. the preparation method of the compound of general formula (1), its step comprises:
(1) compound of difference preparation formula (2) and formula (3): 2, the 5-resorcylic acid reacts with alkyl alcohol that contains 1～16 carbon atom or halogenated alkane, obtains the compound of formula (2); Methyl p-hydroxybenzoate and the functional group of containing 3～12 carbon atoms lay respectively at the chloro-alkenes at chain two ends or bromo alkene at catalyzer, under the condition that alkaline condition and solvent exist, obtain the compound of formula (3):
Formula (2) formula (3)
(2) compound of formula (3) under 70～100 ℃ by the acylating agent acidylate after, the compound of acylate that obtains and formula (2) is at catalyst n, under the effect of N-dimethyl aminopyridine, in basic solvent-20～20 ℃ down reaction obtain the compounds of formula (4):
Formula (4)
R in formula (2), (3) and (4) compound and m are with the compound of claim 1;
(3) compound of formula (4) reacts with the peroxidation agent in organic solvent, and temperature is controlled at 20～60 ℃, obtains the compound of general formula (1).
3. according to the preparation method of the compound of the general formula (1) of claim 2, in mole number, in the described step (1) 1 part 2,5-resorcylic acid and 1～5 part of alkyl alcohol or halogenated alkane reaction, 1 part of methyl p-hydroxybenzoate and 1～5 part of described chloro-alkenes or bromo olefine reaction; The compound of 2 parts of formulas (3) and 2～10 parts of acylation reactions in the described step (2), the compound reaction of 2～5 parts of acylates and 1 part of formula (2); The compound of 1 part of formula (4) and 1～6 part of peroxidation agent reaction in the described step (3).
According to the compound of the general formula (1) of claim 2 or 3 the preparation method, in the step (1) during the compound of preparation formula (2) described alkyl alcohol be propyl carbinol, n-hexyl alcohol, n-Octanol, 1-tridecanol, isooctyl alcohol or 2-tridecanol, described halogenated alkane is the 1-n-butyl bromide, hexyl bromide 1 bromohexane or 1-bromooctane, temperature of reaction is 25～150 ℃, reaction times is 2～15 hours, chloro-alkenes or bromo alkene described in during the compound of preparation formula (3) are chlorallylenes, allyl bromide 98,4-bromo-1-butylene or 6-bromo-1-hexene, described catalyzer is a 18-hat-6-ether, 15-hat-5-ether or dibenzo-18-hat-6-ether, the usage quantity of described catalyzer is 0.005～0.5 part in mole number, described alkali is sodium hydroxide, yellow soda ash, sodium bicarbonate, potassium hydroxide, salt of wormwood or saleratus, described solvent is a deionized water, acetone, pyridine, triethylamine or picoline, temperature of reaction is 40～90 ℃, and the reaction times is 2～48 hours; Acylating agent described in the step (2) is a thionyl chloride, phosphorus trichloride or phosphorus pentachloride, and the usage quantity of described catalyzer is 0.001～0.5 part in mole number, described basic solvent is a pyridine, triethylamine or picoline, the reaction times is 2～48 hours; Peroxidation agent described in the step (3) is the peroxidation 0-chloro-benzoic acid, and described organic solvent is ether, chloroform, ethylene dichloride, acetone or benzene, and the reaction times is 4～200 hours.
5. the compound compositions of general formula (1) is characterized in that by mole number, is made up of compound and 0.5～1.2 part of solidifying agent of 1 part of claim 1.
6. the compound compositions of general formula according to claim 5 (1), it is characterized in that described solidifying agent is diaminodiphenyl-methane, diamino diphenyl sulfone, mphenylenediamine, phthalic anhydride, methyl tetrahydrophthalic anhydride, benzophenone tetracarboxylic dianhydride, resol, polythiol, isocyanic ester, quadrol, two (4-aminocyclohexyl) methane, polymeric amide-polyamines, diaminodiphenyl-methane, diamino diphenyl sulfone or mphenylenediamine.
7. the compound compositions of claim 5 or 6 described general formulas (1) is as the application of electronic package material and shape-memory material.
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| CN104245183A (en) * | 2012-04-27 | 2014-12-24 | 花王株式会社 | Curing agent composition for use in producing mold, use thereof, preparation method therefor, and process for producing mold |
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| CN101195701B (en) * | 2007-11-09 | 2010-09-01 | 中国科学院广州化学研究所 | Epoxy resin shape memory polymer material and method for producing the same |
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| CN104245183A (en) * | 2012-04-27 | 2014-12-24 | 花王株式会社 | Curing agent composition for use in producing mold, use thereof, preparation method therefor, and process for producing mold |
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| CN109913092A (en) * | 2019-03-12 | 2019-06-21 | 江苏苏博特新材料股份有限公司 | The epoxy resin waterproof coating and preparation method thereof of double liquid-crystal structure toughening |
| CN109913092B (en) * | 2019-03-12 | 2022-02-11 | 江苏苏博特新材料股份有限公司 | Double liquid crystal structure toughened epoxy resin waterproof coating and preparation method thereof |
| CN111205249A (en) * | 2020-02-11 | 2020-05-29 | 西北工业大学 | Side chain type liquid crystal epoxy monomer, preparation method thereof and side chain type liquid crystal epoxy resin |
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| CN1259356C (en) | 2006-06-14 |
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