CN1222552A - Epoxy resin adhesive containing rigid mesomorphic radical and flexible chain and its preparation - Google Patents
Epoxy resin adhesive containing rigid mesomorphic radical and flexible chain and its preparation Download PDFInfo
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- CN1222552A CN1222552A CN 98124386 CN98124386A CN1222552A CN 1222552 A CN1222552 A CN 1222552A CN 98124386 CN98124386 CN 98124386 CN 98124386 A CN98124386 A CN 98124386A CN 1222552 A CN1222552 A CN 1222552A
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Abstract
The epoxy resin adhesive includes epoxy resin, dicyandiamide, modifier containing rigid mesomorphic group and flexible chain, mica powder, gas-phase silicon dioxide, barium sulfate and titanium white powder. Compared with common epoxy resin, the said system has obviously lower curing temperature, raised impact toughness and adhering strength, slightly lowered or the same vitrification point. The impact strength is 20-30 KJ/sq m of5-8 times higher, and adhering strength is 222-323 Kg/sq.cm, the vitrification point is 125-162deg.c or no basical reduction, and the modulus at 100 deg.c is 1.13-2.05 GPa. The epoxy resin adhesive is easy to prepare and use and non-toxic.
Description
The present invention relates to the manufacturing of modified epoxy tackiness agent.
Resins, epoxy is as thermoset macromolecule material, though have excellent physical and mechanical properties, chemical resistance, cohesiveness and electrical insulation capability, its shock strength is lower, and resistance to low temperature is relatively poor.Adopt carboxyl end group nitrile rubber (CTBN) and amine end groups nitrile rubber (ATBN) though modified epoxy has partly improved the toughness of Resins, epoxy, but cause the reduction of degree of crosslinking and second-order transition temperature and modulus, in addition, the characteristic of aspects such as heat-resisting, the oxygen aging resistance of curing system and electrical insulation capability descends.The research of making properties-correcting agent (PDMS) with polysiloxane has improved the impact property of epoxy resin cure product, but the second-order transition temperature that causes curing system obviously descends (Zhang Baolong etc., polymer journal 1994, (1), 41).Adopt engineering plastics such as aromaticity polyester, the aromaticity polyetherketone, polysulfones, polyethersulfone, polycarbonate, polyimide and ABS/PC blend (NataraianK.et al., High Perform.Polym.1994,6 (3)) modified epoxy that obtains and liquid crystalline cpd modified epoxy, though can make the tensile strength of Resins, epoxy to a certain extent, shock strength, aspect of performance such as second-order transition temperature and modulus is improved, but it is poor with the consistency of Resins, epoxy, need solvent in most cases, operate inconvenience and be restricted (C.Carfagna, et al, J.Appl.Polym.Sci., 1992,44,1465.).
The purpose of this invention is to provide a kind of epoxy resin binder that contains rigidity mesomorphic group and flexible chain properties-correcting agent and preparation method thereof, it is that materials such as liquid epoxies, dicyandiamide, filler are mixed with a kind of novel epoxy resin binder, this tackiness agent can be in middle low-temperature curing, adhesives had both had high glass transition, high-modulus, high-intensity characteristic, had good impelling strength and bonding strength again.In addition, it is simple to operate, to the human body toxicological harmless.
Main component of the present invention and proportioning (weight) are as follows:
100 parts of liquid epoxiess
4～6 parts of dicyandiamides
10～40 parts of properties-correcting agent
12～15 parts of mica powders
2～5 parts of silicon-dioxide
3～5 parts in barium sulfate
3～5 parts of titanium dioxides
Concrete preparation process of the present invention:
At first press formula rate with a certain amount of dicyandiamide, filler (mica powder, silicon-dioxide, barium sulfate and titanium dioxide) in 60 ℃ vacuum drying oven dry 24 hours, pulverize and stir.Take by weighing a certain amount of Resins, epoxy then.Add dicyandiamide-filler mixture and a certain amount of properties-correcting agent in Resins, epoxy, stirring gets final product.Preparation shock strength test sample needed under 60 ℃ of vacuum de-bubbled 3 hours, with the micro bubble of bringing in the elimination air.The adhesives of preparation general thickness does not need de-bubbled under the vacuum, directly solidifies to get final product that (whole process need not add any solvent! ).The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Properties-correcting agent among the present invention is synthetic through a series of step, at first adopt ordinary method to prepare terephthaloyl dioxydibenze formic acid hydroxyl ethyl ester, (polyether chain is polyoxyethylene glycol or propylene oxide polyethers to the polyether-polyurethane performed polymer, molecular weight is 200～4000), it comprises following concrete steps: with terephthaloyl dioxydibenze formic acid hydroxyl ethyl ester (TOBE), the polyether-polyurethane performed polymer, (mol ratio is 1: 2) reacted 3-6 hour down in 60～90 ℃ in dimethyl formamide solution, reduce to room temperature, feed dimethylamine gas and not till the isocyanato group containing, obtain thick liquid to the solution.The concrete synthesis technique step of each reaction intermediate and final product is described in detail as follows: the following (J.T.Guthrie of synthetic route of (one) terephthaloyl dioxydibenze acyl chlorides (TOBC), A.Mortonand E Nield J.Oil and Colour Chem.Associ., 1992,1,16):
(1) terephthaloyl dioxydibenze formic acid (TOBA) is synthetic: add 0.6M NaOH solution and P-hydroxybenzoic acid, stirring and dissolving in there-necked flask; P-phthaloyl chloride is dissolved in CCl
4In, being added drop-wise in the reaction solution under the room temperature, stirring velocity is very fast.White precipitate appears in reaction solution, by the transparent muddiness that becomes.Suction filtration after having reacted, the gained white precipitate is soaked in 2MHCl solution, suction filtration, washing, drying gets white products, and productive rate is 89.8%.
(2) terephthaloyl dioxydibenze acyl chlorides (TOBC) is synthetic: the electronic stirring of device, reflux condensing tube, dropping funnel and HCl gas absorbing device on there-necked flask, TOBA is added in the reaction flask, and pour SOCl into
2, stirring and refluxing to reaction solution clarification stops under water-bath.Heat filtering is removed insolubles in the reaction solution.The filtrate freezing and crystallizing, suction filtration gets the white needles product.With the chloroform recrystallization that drying is crossed, end product is a white needle-like crystals, productive rate 60%.(2) terephthaloyl dioxydibenze formic acid hydroxyl ethyl ester (TOBE) is synthetic:
Install electronic stirring on there-necked flask, reflux condensing tube adds TOBC, newly steams ethylene dichloride, stirs, and heating for dissolving is transparent clear liquid, adds ethylene glycol, the catalyzer pyridine, and 50～90 ℃ were reacted 3～6 hours down.Stopped reaction is chilled to room temperature, suction filtration, and washing gets white powdery solid, and productive rate can reach 94%, records its fusing point through differential calorimetric scanning method (DSC method) and is～210 ℃.(3) the polyether-polyurethane performed polymer synthetic (Sandler SR, Berg FR.J Appl Polym Sci, 1965,9:
3909)：
By the propylene oxide polyethers (PPG) of different molecular weight, polyoxyethylene glycol (PEG), the synthetic polyether-polyurethane performed polymer of flexible spacer that contains of isocyanic ester (by isocyanato in the chemical titration monitoring system (terminal point of content control prepolymer reaction NCO)).
Wherein R is-CH
3Or-H.When R is-CH
3The time, abbreviating P-as and give aggressiveness, R is-during H, abbreviates E-as and gives aggressiveness.(4) contain epoxide resin reactive plasticized modifier (LCSU) synthetic of mesomorphic group and flexible chain:
(flexible chain is polyoxyethylene glycol or propylene oxide polyethers with TOBE, polyether-polyurethane performed polymer, molecular weight is 200～4000), secondary amine is raw material, dimethyl formamide is a solvent, the synthetic multi-functional epoxy resin active modifier that has containing of following structure of mesomorphic unit, flexible chain, reaches the end active group is called for short LCSU.When flexible spacer is the propylene oxide polyethers, be designated as LCSU
PX, LCSU when flexible spacer is the oxyethane polyethers
EX, X is the molecular weight of flexible chain, synthetic route is as follows:
Product (3) is the dense mucus of shallow white, and productive rate can reach 96～98%, and product (4) abbreviates LCSU as, for yellow to the dense mucus of brown xanchromatic, productive rate can reach 95～97%.Table 1 is LCSU
PXAnd LCSU
EXPhysical properties.
The physicals of table 1. different molecular weight properties-correcting agent
| Product | Molecular weight | Viscosity (handkerchief second) | Outward appearance | Productive rate (%) |
| ????LCSU P1000????LCSUP 2000????LCSUP 4000????LCSU E1000????LCSU E600????LCSU E400????LCSU E200 | ????3280 ????5280 ????9280 ????3280 ????2480 ????2080 ????1680 | ????194 ????334 ????676 ????184 ????175 ????135 ????100 | Faint yellow faint yellow yellow | ????96 ????95 ????97 ????97 ????95 ????96 ????95 |
Characteristics of the present invention are very tangible.Resins, epoxy is that a class has superior mechanical intensity, electrical insulating property is good, shrinkability is little, bonding strength is high thermosetting material.But back material matter is crisp, shock strength is low and the stress crack resistant ability because the highdensity network structure of cured product causes solidifying, thereby has limited its application in a lot of fields.So Resins, epoxy toughness reinforcing has very important meaning.The present invention can make the shock strength of Resins, epoxy improve nearly five to octuple (20～30KJ/m
2), the bonding strength (222～323Kg/cm that is enhanced about more than once
2), second-order transition temperature does not reduce (125～162 ℃) substantially, and the modulus under 100 ℃ is 1.13～2.05GPa, is a kind of effectively high tenacity, high-adhesive-strength, heat-staple high-modulus jointing material.
Substantive distinguishing features that the present invention gives prominence to and marked improvement can be embodied from following embodiment, but they are not that the present invention is imposed any restrictions.
Example 1: properties-correcting agent synthetic
(1). synthesizing of terephthaloyl dioxydibenze formic acid (TOBA): in there-necked flask, add 400ml, 0.6MNaOH solution, 27.0 gram P-hydroxybenzoic acid, stirring and dissolving.17 gram p-phthaloyl chlorides are dissolved in 170mlCCl
4In, be added drop-wise in the reaction solution under the room temperature.White precipitate appears in reaction solution, by the transparent muddiness that becomes.Suction filtration after having reacted, gained white precipitate are soaked in 4M HCl solution, suction filtration, and washing, drying obtains white products, and productive rate is 89.8%.
(2). synthesizing of terephthaloyl dioxydibenze acyl chlorides (TOBC): the electronic stirring of device on there-necked flask, reflux condensing tube, dropping funnel and HCl gas absorbing device add 20 gram TOBA in the reaction flasks, pour 300mlSOCl into
2, stirring and refluxing to reaction solution clarification stops under water-bath.Heat filtering is removed insolubles in the reaction solution.The filtrate freezing and crystallizing, suction filtration gets the white needles product.With the chloroform recrystallization that drying is crossed, end product is a white needle-like crystals, productive rate 60%.
(3). terephthaloyl dioxydibenze formic acid hydroxyl ethyl ester (TOBE) is synthetic: the electronic stirring of device on there-necked flask, reflux condensing tube, add 45.5 gram TOBC, the new ethylene dichloride 300ml that steams stirs, and heating for dissolving is transparent clear liquid, add 7.0 gram ethylene glycol, the 1ml pyridine, 80 ℃ of temperature of reaction, 4 hours reaction times.Stopped reaction is chilled to room temperature, suction filtration, and washing gets white powdery solid, and productive rate can reach 94%, and recording its fusing point by differential calorimetric scanning method (DSC) is 210 ℃.
(4) .P-1000 gives the synthetic of aggressiveness: in 1 liter four-hole bottle, adding molecular weight is 1000 propylene oxide polyethers, 500 grams, tolylene diisocyanate 174 grams, and 90 ℃ of temperature of reaction in about 4 hours of reaction times, obtain light yellow viscous liquid.
(5) .LCSU
P1000Synthetic: 1 liter have whipping appts, a N
2In the four-hole bottle of conduit, thermometer, prolong, add the TOBE50.6 gram, P-1000 performed polymer 270 grams, dimethyl formamide 400ml, temperature of reaction is 80 ℃, react after 4 hours, be cooled to room temperature, feed about 60 grams (is that raw material adds hot preparation with 35% industrial dimethylamine agueous solution 200ml) of dimethylamine gas, obtaining molecular weight is 3280, viscosity is 194 handkerchiefs. the light yellow viscous liquid of second is designated as LCSU
P1000, productive rate 96%.
Example 2: filler 25 grams (wherein mica powder 13 grams, silicon-dioxide 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
P100010Gram joins to stir in the 100 gram Resins, epoxy and gets final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.Test result sees Table 2.
Annotate: modulus and second-order transition temperature are measured with the Japanese TOYO BALDWIN DDV-of company II-EA type dynamic viscoelasticity spectrum, temperature rise rate: 2 ℃/minute, and frequency: 110 hertz; Curing reaction temperature adopts the Shanghai CDR-1 of balance equipment factory type DSC to measure experiment condition: differential thermal compensation ± 21mJ/sec, and atmosphere is air, with before doing temperature correction; Shock strength adopts the Chengde CHARPRY XCJ-500 of experimental machine factory type impact experiment machine, presses the GB-1043-79 standard test; Shearing resistance is pressed the HG-151-65 standard, homemade electronic universal tester WD)-10 types, draw speed 5mm/min., tension load 10,000 newton.
Table 2 example 2 solidifies the sample physicals
| Modulus second-order transition temperature shock strength shearing resistance under 100 ℃ of the curing reaction temperatures | ????160℃ ???????1.41GPa ????157℃ ???????20.0KJ/m 2????222Kg/cm 2 |
Example 3: filler 25 grams (wherein mica powder 13 grams, silicon-dioxide 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
P100030 grams join to stir in the 100 gram Resins, epoxy and get final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Table 3 example 3 solidifies sample performance
| Modulus second-order transition temperature shock strength bonding strength under 100 ℃ of the curing reaction temperatures | ????152℃ ???????1.13GPa ????148℃ ???????25.5KJ/m 2????299Kg/cm 2 |
Example 4: filler 25 grams (wherein mica powder 13 grams, aerosil 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
P200010 grams join to stir in the 100 gram Resins, epoxy and get final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Table 4 example 4 solidifies sample performance
| Modulus second-order transition temperature shock strength bonding strength under 100 ℃ of the curing reaction temperatures | ????171℃ ???????1.17GPa ????162℃ ???????29.0KJ/m 2????242Kg/cm 2 |
Example 5: filler 25 grams (wherein mica powder 13 grams, silicon-dioxide 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
P200020 grams join to stir in the 100 gram Resins, epoxy and get final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Table 5 example 5 solidifies sample performance
| Modulus second-order transition temperature shock strength bonding strength under 100 ℃ of the curing reaction temperatures | ????168℃ ???????1.13GPa ????161℃ ???????27.8KJ/m 2????322Kg/cm 2 |
Example 6: filler 25 grams (wherein mica powder 13 grams, silicon-dioxide 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
E100010 grams join to stir in the 100 gram Resins, epoxy and get final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Table 6 example 6 solidifies sample performance
| Modulus second-order transition temperature shock strength bonding strength under 100 ℃ of the curing reaction temperatures | ????153℃ ???????2.05GPa ????154℃ ???????33.4KJ/m 2????259Kg/cm 2 |
Example 7: filler 25 grams (wherein mica powder 13 grams, silicon-dioxide 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
E100020 grams join to stir in the 100 gram Resins, epoxy and get final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Table 7 example 7 solidifies sample performance
| Modulus second-order transition temperature shock strength bonding strength under 100 ℃ of the curing reaction temperatures | ????149℃ ???????2.05GPa ????133℃ ???????32.6KJ/m 2????261Kg/cm 2 |
Example 8: filler 25 grams (wherein mica powder 13 grams, silicon-dioxide 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
E60010 grams join to stir in the 100 gram Resins, epoxy and get final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Table 8 example 8 solidifies sample performance
| Modulus second-order transition temperature shock strength bonding strength under 100 ℃ of the curing reaction temperatures | ????150℃ ???????1.66GPa ????156℃ ???????30.3KJ/m 2????222Kg/cm 2 |
Example 9: filler 25 grams (wherein mica powder 13 grams, silicon-dioxide 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
E60020 grams join to stir in the 100 gram Resins, epoxy and get final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Table 9 example 9 solidifies sample performance
| Modulus second-order transition temperature shock strength bonding strength under 100 ℃ of the curing reaction temperatures | ????142℃ ???????1.57GPa ????135℃ ???????30.5KJ/m 2????245Kg/cm 2 |
Example 10: filler 25 grams (wherein mica powder 13 grams, silicon-dioxide 2 grams, barium sulfate 5 grams, titanium dioxide 5 grams), dicyandiamide 6 grams are according to the resulting properties-correcting agent LCSU of example 1 preparation method
E60030 grams join to stir in the 100 gram Resins, epoxy and get final product.Sample is used in the test of preparation shock strength, and de-bubbled is 3 hours under 60 ℃ of vacuum.The preparation bonding sample, directly solidify bonding intact back.The sample condition of cure: 120 ℃ 2 hours, 140 ℃ 2 hours, last 160 ℃ 2 hours.
Table 10 example 10 solidifies sample performance
| Modulus second-order transition temperature shock strength bonding strength under 100 ℃ of the curing reaction temperatures | ????136℃ ???????1.47GPa ????125℃ ???????30.5KJ/m 2????247Kg/cm 2 |
Claims (3)
1. epoxy resin binder that contains rigidity mesomorphic group and flexible chain properties-correcting agent is characterized in that its weight proportion is:
100 parts of Resins, epoxy
4～6 parts of dicyandiamides
10～40 parts of properties-correcting agent
12～15 parts of mica powders
2～5 parts of silicon-dioxide
3～5 parts in barium sulfate
3～5 parts of titanium dioxides
2. the said preparation method who contains the epoxy resin binder of rigidity mesomorphic group and flexible chain properties-correcting agent of claim 1, it is characterized in that it is through following concrete steps: at first press formula rate with dicyandiamide, filler in vacuum drying oven 60 ℃ dry 24 hours down, pulverize and stir; Take by weighing the Resins, epoxy of metering then; Add dicyandiamide-filler mixture and properties-correcting agent in Resins, epoxy, stirring gets final product.
3. the preparation method of the said properties-correcting agent of claim 1, at first adopt ordinary method to prepare terephthaloyl dioxydibenze formic acid hydroxyl ethyl ester, the polyether-polyurethane performed polymer, it is characterized in that it is through following concrete steps: with terephthaloyl dioxydibenze formic acid hydroxyl ethyl ester, (polyether chain is polyoxyethylene glycol or propylene oxide polyethers to the polyether-polyurethane performed polymer, molecular weight is 200～4000), (mol ratio is 1: 2) reacted 3-6 hour down in 60～90 ℃ in dimethyl formamide solution, reduce to room temperature, feed dimethylamine gas and not till the isocyanato group containing, obtain thick liquid to the solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98124386A CN1089105C (en) | 1998-11-09 | 1998-11-09 | Epoxy resin adhesive containing rigid mesomorphic radical and flexible chain and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98124386A CN1089105C (en) | 1998-11-09 | 1998-11-09 | Epoxy resin adhesive containing rigid mesomorphic radical and flexible chain and its preparation |
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| Publication Number | Publication Date |
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| CN1222552A true CN1222552A (en) | 1999-07-14 |
| CN1089105C CN1089105C (en) | 2002-08-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382546A (en) * | 2010-09-06 | 2012-03-21 | 张子鹏 | Special modified solvent-free epoxy paint for glass reinforced plastic |
| CN101679579B (en) * | 2007-06-20 | 2012-05-30 | 陶氏环球技术公司 | Crash durable epoxy adhesives with very low sensitivity to temperature variations |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5647445A (en) * | 1979-09-27 | 1981-04-30 | Hitachi Chem Co Ltd | Epoxy resin composition |
| EP0578613B1 (en) * | 1992-07-09 | 2000-07-12 | Ciba SC Holding AG | Curable epoxy resin suspensions |
| JPH06207154A (en) * | 1993-01-08 | 1994-07-26 | Murata Mfg Co Ltd | One pack type thermosetting adhesive, piezoelectric vibration gyro using the same and method of adhesion |
-
1998
- 1998-11-09 CN CN98124386A patent/CN1089105C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679579B (en) * | 2007-06-20 | 2012-05-30 | 陶氏环球技术公司 | Crash durable epoxy adhesives with very low sensitivity to temperature variations |
| CN102382546A (en) * | 2010-09-06 | 2012-03-21 | 张子鹏 | Special modified solvent-free epoxy paint for glass reinforced plastic |
| 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 |
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| CN1089105C (en) | 2002-08-14 |
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