CN104119642A - Hydantoin epoxy resin modified by nano nitrile rubber and production method of hydantoin epoxy resin - Google Patents
Hydantoin epoxy resin modified by nano nitrile rubber and production method of hydantoin epoxy resin Download PDFInfo
- Publication number
- CN104119642A CN104119642A CN201310153590.7A CN201310153590A CN104119642A CN 104119642 A CN104119642 A CN 104119642A CN 201310153590 A CN201310153590 A CN 201310153590A CN 104119642 A CN104119642 A CN 104119642A
- Authority
- CN
- China
- Prior art keywords
- epoxide resin
- nanometer
- glycolylurea epoxide
- butadiene rubber
- acrylonitrile butadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a hydantoin epoxy resin modified by nano nitrile rubber and a production method of the hydantoin epoxy resin. The hydantoin epoxy resin modified by nano nitrile rubber comprises the following components in percentage by weight: 8-15% of nano nitrile rubber, 72-78% of hydantoin epoxy resin, 3-4% of a dispersant, 3-4% of a coupling agent, 3-4% of an accelerant, 1-2% of a defoamer and 1-2% of a flatting agent. The production method of the modified hydantoin epoxy resin comprises the following steps: mixing the nano nitrile rubber with the dispersant; after activation, carrying out anchored stirring and dispersion; then pre-leaching with other components; then, primarily grinding and finely dispersing; and carrying out secondary paddle stirring and finely dispersing. The hydantoin epoxy resin modified by nano nitrile rubber, which is disclosed by the invention, has high rigidity, high toughness, high temperature resistance, high corrosion resistance, high weather resistance and high insulating property while maintaining other performances.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of modified epoxy and production method thereof, the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of espespecially a kind of nanometer and production method thereof.
Background technology
Epoxy resin (hereinafter to be referred as EP) refers to the organic high molecular compound that contains more than two and two epoxide group in molecule, and its structure is to contain active epoxide group in molecular chain as feature.This makes them can form with polytype solidifying agent generation crosslinking reaction insoluble, the molten cancellated superpolymer of three-dimensional that has, and feature becomes now most widely used resin system in some type materials thus.General EP as thermosetting resin due to a series of physics and chemical properties such as intensity is high, corrosion-resistant, anti-aging, lightweight, easy processing, more and more be widely used in glue class base-material, the every field such as sealed insulation, the vehicles, building structure, fiber composite, military project aviation are one of important materials of industry now.Simultaneously, self but has very large defect general common EP, although be mainly manifested in the highly cross-linked rear very high rigidity that has, after solidifying, the low fragility of toughness is large, under low temperature, fragility is larger, and its shock strength, fatigue property, resistance toheat also all exist some drawbacks simultaneously.For example applying electronic electrician waters after the casting material demoulding product cracking and scraps; National reservoir dam can produce crack because be subject to earth movement and expanding with heat and contract with cold etc. affects body surface, after repairing, due to poor toughness only 2～3 years in work-ing life, has caused the significant wastage of national manpower, financial resources with EP casting.Due to these drawbacks that general EP exists, be therefore extremely restricted in many Application Areass.In order to meet the requirement stricter, harsh to material of current each industry and new and high technology, must solve the above-mentioned defect of EP.General EP being carried out to tough-increased and reinforced modification and improve its integrated performance index, is an important topic of current epoxy industry.At present, the domestic and international toughness reinforcing a variety of modes that have, in trial-production charter, mention, initial stage adopts the carboxylate of long molecular chain toughness reinforcing, although it can reduce string stress and the initial stage does not ftracture, because these long molecular chain carboxylates are free between curing epoxy resin molecule and do not produce crosslinked action.As time goes on can produce by interior transport phenomena outwardly, finally cause embrittlement ftracture and lost efficacy.Also have employing resinous blending mid-term, the means of rubber blending are carried out toughening modifying to EP, because many reason effects are not clearly yet, and the unstable factor such as even expensive of complex process, quality and hinder its development.The more method for toughening of current employing has: the method for the toughness reinforcing EP of island structure, the method for the toughness reinforcing EP of interpenetrating(polymer)networks, by the method for nano inorganic particle toughening EP, polar rubber as the method for thiorubber, end carboxyl butyronitrile or the toughness reinforcing EP of hydroxy'terminated butadiene nitrile rubber etc.In these methods, some rests on laboratory stage (as: method of the toughness reinforcing EP of interpenetrating(polymer)networks), although some toughening effect is pretty good, but some good performance characteristics of having sacrificed again EP (as: add after island structure toughness reinforcing, shock-resistant toughness reinforcing successful improves, but reduce heat-drawn wire and made it to have lost competitive power, and for example add the polar rubber certain successful of EP as toughness reinforcing in thiorubber blending, but heat-drawn wire is declined, and expensive, end carboxyl butyronitrile or hydroxy'terminated butadiene nitrile rubber price are in the hundreds of unit per kilogram price such to several thousand yuan of per kilograms), common product is difficult to adopt.Nano inorganic particle toughening EP is nearest study hotspot, but mostly rest on experimental stage from present document, tracing it to its cause is that the consistency of nano inoganic particle and glycolylurea epoxide resin is bad, employing as too complicated in intercalation technique scheme, and fund input is large and quality stability is poor.
Summary of the invention
For the shortcoming of the market requirement and prior art, the object of the present invention is to provide a kind ofly to there is high rigidity, high tenacity, high temperature tolerance, highly corrosive, high-weatherability, high-insulativity and particularly overcome the high acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer that makes the drawback that Application Areas is subject to certain limitation of viscosity after bisphenol A type epoxy resin modification.The acrylonitrile butadiene rubber modified glycolylurea epoxide resin of this nanometer has been widened Application Areas, has facilitated construction, also can make other performance significantly improve simultaneously.
The present invention also provides the production method of the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of this nanometer.
The object of the invention is to realize in the following manner:
A kind of nanometer acrylonitrile butadiene rubber modified epoxy resin, this modified epoxy comprises following component according to weight percent: nanometer paracril 8-15%, glycolylurea epoxide resin 72-78%, dispersion agent 3-4%, coupling agent (claiming again surface treatment agent) 3-4%, promotor 3-4%, defoamer 1-2%, flow agent 1-2%.Above-mentioned each composition weight sum is 100%.
Preferably nanometer acrylonitrile butadiene rubber modified epoxy resin comprises following component according to weight percent: nanometer paracril 10-15%, glycolylurea epoxide resin 72-76%, dispersion agent 3-4%, coupling agent (claiming again surface treatment agent) 3-4%, promotor 3-4%, defoamer 1-2%, flow agent 1-2%.Above-mentioned each composition weight sum is 100%.
Most preferably nanometer acrylonitrile butadiene rubber modified epoxy resin comprises following component according to weight percent: nanometer paracril 12%, epoxy resin 75%, dispersion agent 3%, coupling agent (claiming again surface treatment agent) 3%, promotor 3%, defoamer 2%, flow agent 2%.
The glycolylurea epoxide resin that the present invention adopts is preferably glycolylurea epoxide resin MHR070 or glycolylurea epoxide resin MHR-154.
Nano material (claims again ultrafine particulate, ultrafine powder) be a kind of typical systems in atom a small bundle of straw, etc. for silkworms to spin cocoons on and objective object boundary transitional region, its structure had both been different from body block of material, also be different from single atom, its special structure makes it have surface effects, volume effect, quantum tunneling effect etc., have the physics and chemistry characteristic of series of novel, the nanometer paracril (nano material) that the present invention adopts is nanometer paracril VP-401 preferably.
The dispersion agent adopting in the present invention is preferably acid dimethyl sodium.In the present invention, this dispersant adsorption is in EP liquid---nanometer paracril VP-401 solid interface, can significantly reduce interfacial free energy, and cause pressed powder rubber evenly spread in the EP of liquid and make it not reassociate.And the present invention preferably adopts acid dimethyl sodium as dispersion agent, after testing prove, use this dispersion agent not only to strengthen the dispersion effect of nano material, effectively chelating the interface combination of material.
Coupling agent (being called again surface treatment agent) is the material two kinds of very large material mortise that are originally difficult for combination of nature difference being got up by chemistry and (or) physical action.It not only makes filled polymers closely be connected and reach good physical strength, and filler obviously reduces through the diameter of the processing polymkeric substance of coupling agent, can make the dispersiveness of filler in polymkeric substance, the mobility of material be improved.In the present invention, coupling agent (claiming again surface treatment agent) is preferably isopropyl triisostearoyl titanate, and this coupling agent can effectively improve mechanical property, apparent mass and the processing characteristics of modification EP derived product in the present invention.
In the present invention, promotor preferred accelerators DMP-30 or trolamine, can make the EP strengthening physical strength after modification, increases solidification effect, promotes curing reaction speed.Raw material of the present invention is commercially available obtaining all.
Owing in process of production material high-speed being stirred and high speed rotating strong shear, air a large amount of in this process are formed countless small bubbles in material by winding up, to material curing molding, reduce its physical strength thereby can produce cellular porosity.To this, the defoamer using in component of the present invention is preferably dimethyl siloxane, can effectively eliminate the bubble of product.
Conventionally after epoxy resin modification, easily viscosity raises, and Application Areas is very restricted, and adds the organic-silicon-modified polysiloxane of flow agent to overcome the higher problem of EP viscosity, and ensure that other performances can not decline simultaneously in the present invention's formula.
The preparation method of the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of above-mentioned nanometer comprises the following steps:
The first step: by nanometer paracril and dispersant, carry out anchor formula after activated and stir pre-dispersedly, pre-dispersed condition is: 30～40 DEG C of temperature controls, mixing speed per minute 800-1000 turns, jitter time 2 minutes;
Second step: by the material obtaining by component ratio add glycolylurea epoxide resin and, that coupling agent, defoamer, flow agent and promotor are carried out preimpregnation is molten, the molten condition of preimpregnation is: 20～40 DEG C of temperature, time 5-6 hour;
The 3rd step: grind finely dividedly to soaking material three-roller after molten, make three-roller discharging 60-70 kilogram per hour;
The 4th step: the material after disperseing is carried out to slurry formula and stir fine dispersion, disperse to finish rear standing 24-48 hour;
The 5th step: the material after leaving standstill is carried out to slurry formula for the second time and stir fine dispersion, make finished product.
Preferably twice slurry formula stirs fine dispersion condition: mixing speed per minute 100-150 turns, jitter time 4-5 hour, and 30～50 DEG C of temperature controls,
The raw material that the present invention adopts stirs pre-dispersed through an anchor formula, once grind finely divided, secondary slurry formula stirs fine dispersion, under the effect of external force, agglomeration disappears, and has reached excellent dispersion effect, simultaneously in the process of physical dispersion, also add chemical dispersant, further optimized dispersion effect.
At finely divided S90 or the S60 three-roller of using of grinding of the present invention.
The invention has the beneficial effects as follows: the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer of the present invention has high rigidity, high tenacity, high temperature tolerance, highly corrosive, high-weatherability and high insulating property; And the present invention can not make again other performance reduce in ensureing the high rigidity of the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer, high tenacity, high temperature tolerance, highly corrosive, high-weatherability and high insulating property.Glycolylurea epoxide resin shock strength after modification of the present invention is by 9.7KJ/m
2(performance of glycolylurea epoxide resin MHR070) brings up to 44.4KJ/m
2heat-drawn wire is brought up to 191 DEG C of left and right by 180.1 DEG C (performances of glycolylurea epoxide resin MHR070), second-order transition temperature is brought up to 217.7 DEG C by 197.7 DEG C (performances of glycolylurea epoxide resin MHR070), and elongation at break brings up to 10.2% by 3.1% (performance of glycolylurea epoxide resin MHR070).And product is nontoxic, harmless, nonflammable, long quality-guarantee period, in production process, do not produce waste water,waste gas and industrial residue, technical difficulty is little, cost of investment is low, the construction period is short, almost without environmental issue, be real environmentfriendly products.
Embodiment
Below with reference to embodiment, the present invention will be further described, and embodiment is only for technical scheme of the present invention is described, and non-limiting the present invention.
Embodiment 1
Composition weight proportioning:
Nanometer paracril VP-401 (Beijing Chemical Research Institute's production) 8-13%, epoxy resin MHR-154 (Wuxi Meihua Chemical Co., Ltd.'s production) 74-78%, acid dimethyl sodium 3-4%, isopropyl triisostearoyl titanate 3-4%, altax P-303-4%, dimethyl siloxane 1-2%, organic-silicon-modified polysiloxane (Changzhou is thought Nore Chemical Co., Ltd. and produced) 1-2%.
Production method:
The first step: by nanometer paracril and dispersant in component, carry out anchor formula after activated and stir pre-dispersedly, pre-dispersed condition is: 30～40 DEG C of temperature controls, mixing speed per minute 800-1000 turns, jitter time 2 minutes;
Second step: the material that the first step is obtained by component ratio add glycolylurea epoxide resin and coupling agent, defoamer, flow agent, that promotor is carried out preimpregnation is molten; The molten condition of preimpregnation is: 20～40 DEG C of temperature, time 5-6 hour;
The 3rd step: it is finely divided that the material after molten to second step preimpregnation adopts S60 three-roller to grind, and makes S60 three-roller discharging 60-70 kilogram per hour;
The 4th step: the material after the 3rd step is disperseed carries out slurry formula and stirs fine dispersion, and mixing speed per minute 100 turns, and 30～50 DEG C of temperature controls disperse 4-5 hour, disperses to finish latter standing 48 hours;
The 5th step: the material after the 4th step is carried out to slurry formula and stir fine dispersion, mixing speed per minute 100 turns, 30～50 DEG C of temperature controls disperse 4-5 hour, after disperseing to finish, get product.
Embodiment 2
Composition weight proportioning:
Nanometer paracril VP-401 (Beijing Chemical Research Institute's production) 10-15%, epoxy resin MHR070 (Wuxi Meihua Chemical Co., Ltd.'s production) 72-76%, acid dimethyl sodium 3-4%, isopropyl triisostearoyl titanate 3-4%, trolamine 3-4%, dimethyl siloxane 1-2%, organic-silicon-modified polysiloxane (Changzhou is thought Nore Chemical Co., Ltd. and produced) 1-2%.
Production method:
The first step: by nanometer paracril and dispersant in component, carry out anchor formula after activated and stir pre-dispersedly, pre-dispersed condition is: 30～40 DEG C of temperature controls, mixing speed per minute 800-1000 turns, jitter time 2 minutes;
Second step: the material that the first step is obtained by component ratio add glycolylurea epoxide resin and coupling agent, defoamer, flow agent, that promotor is carried out preimpregnation is molten; The molten condition of preimpregnation is: 25 DEG C of temperature, time 5-6 hour;
The 3rd step: it is finely divided that the material after molten to second step preimpregnation adopts S60 three-roller to grind, and makes S60 three-roller discharging 60-70 kilogram per hour;
The 4th step: the material after the 3rd step is disperseed carries out slurry formula and stirs fine dispersion, and mixing speed per minute 150 turns, and 30～50 DEG C of temperature controls disperse 4-5 hour, disperses to finish latter standing 24 hours;
The 5th step: the material after the 4th step is carried out to slurry formula and stir fine dispersion, mixing speed per minute 150 turns, 30～50 DEG C of temperature controls disperse 4-5 hour, after disperseing to finish, get product.
Embodiment 3
Composition weight proportioning:
Nanometer paracril VP-401 (Beijing Chemical Research Institute's production) 12%, epoxy resin MHR070 (Wuxi Meihua Chemical Co., Ltd.'s production) 75%, acid dimethyl sodium 3%, isopropyl triisostearoyl titanate 3%, trolamine 3%, dimethyl siloxane 2%, organic-silicon-modified polysiloxane (Changzhou is thought Nore Chemical Co., Ltd. and produced) 2%.
Production method:
The first step: by nanometer paracril and dispersant in component, carry out anchor formula after activated and stir pre-dispersedly, pre-dispersed condition is: 30～40 DEG C of temperature controls, mixing speed per minute 800-1000 turns, jitter time 2 minutes;
Second step: the material that the first step is obtained by component ratio add glycolylurea epoxide resin and coupling agent, defoamer, flow agent, that promotor is carried out preimpregnation is molten; The molten condition of preimpregnation is: 25 DEG C of temperature, time 5-6 hour;
The 3rd step: it is finely divided that the material after molten to second step preimpregnation adopts S90 three-roller to grind, and makes S90 three-roller discharging 60-70 kilogram per hour;
The 4th step: the material after the 3rd step is disperseed carries out slurry formula and stirs fine dispersion, and mixing speed per minute 150 turns, and 30～50 DEG C of temperature controls disperse 4-5 hour, disperses to finish latter standing 24 hours;
The 5th step: the material after the 4th step is carried out to slurry formula and stir fine dispersion, mixing speed per minute 150 turns, 30～50 DEG C of temperature controls disperse 4-5 hour, after disperseing to finish, get product.
The acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer preparing according to embodiment method contrasts as shown in table 1 with prior art Properties of Epoxy Resin:
Table 1
Claims (10)
1. the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer, is characterized in that the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of this nanometer comprises following component according to weight percent: nanometer paracril 8-15%, glycolylurea epoxide resin 72-78%, dispersion agent 3-4%, coupling agent 3-4%, promotor 3-4%, defoamer 1-2%, flow agent 1-2%.
2. the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer according to claim 1, is characterized in that described glycolylurea epoxide resin is glycolylurea epoxide resin MHR070 or glycolylurea epoxide resin MHR-154.
3. the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer according to claim 1, is characterized in that described nanometer paracril is nanometer paracril VP-401.
4. the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer according to claim 1, is characterized in that described dispersion agent is acid dimethyl sodium.
5. the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer according to claim 1, is characterized in that described coupling agent is isopropyl triisostearoyl titanate.
6. the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer according to claim 1, is characterized in that described promotor is altax P-30 or trolamine.
7. the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer according to claim 1, is characterized in that described defoamer is dimethyl siloxane.
8. the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer according to claim 1, is characterized in that described flow agent is organic-silicon-modified polysiloxane.
9. a preparation method for the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer claimed in claim 1, is characterized in that the method comprises the following steps:
The first step: by nanometer paracril and dispersant, carry out anchor formula after activated and stir pre-dispersedly, pre-dispersed condition is: 30～40 DEG C of temperature controls, mixing speed per minute 800-1000 turns, jitter time 2 minutes;
Second step: add glycolylurea epoxide resin, coupling agent, defoamer, flow agent and promotor to carry out preimpregnation by component ratio the material obtaining molten, the molten condition of preimpregnation is: 20～40 DEG C of temperature, time 5-6 hour;
The 3rd step: grind finely dividedly to soaking material three-roller after molten, make three-roller discharging 60-70 kilogram per hour;
The 4th step: the material after disperseing is carried out to slurry formula and stir fine dispersion, disperse to finish rear standing 24-48 hour;
The 5th step: the material after leaving standstill is carried out to slurry formula for the second time and stir fine dispersion, make finished product.
10. the preparation method of the acrylonitrile butadiene rubber modified glycolylurea epoxide resin of nanometer according to claim 9, is characterized in that described slurry formula stirs fine dispersion condition and is: mixing speed per minute 100-150 turns, jitter time 4-5 hour, 30～50 DEG C of temperature controls.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310153590.7A CN104119642A (en) | 2013-04-28 | 2013-04-28 | Hydantoin epoxy resin modified by nano nitrile rubber and production method of hydantoin epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310153590.7A CN104119642A (en) | 2013-04-28 | 2013-04-28 | Hydantoin epoxy resin modified by nano nitrile rubber and production method of hydantoin epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104119642A true CN104119642A (en) | 2014-10-29 |
Family
ID=51765292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310153590.7A Pending CN104119642A (en) | 2013-04-28 | 2013-04-28 | Hydantoin epoxy resin modified by nano nitrile rubber and production method of hydantoin epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104119642A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479069A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of polystyrene microsphere composite for laser sintering and moulding and preparation method thereof |
-
2013
- 2013-04-28 CN CN201310153590.7A patent/CN104119642A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479069A (en) * | 2015-08-27 | 2017-03-08 | 合肥杰事杰新材料股份有限公司 | A kind of polystyrene microsphere composite for laser sintering and moulding and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108504250B (en) | Epoxy resin composite wear-resistant coating and preparation method thereof | |
| CN109265922B (en) | High-toughness autocatalytic epoxy resin and preparation method thereof | |
| CN103965590B (en) | Epoxy resin composite material of a kind of coordination plasticizing and preparation method thereof | |
| CN109135187B (en) | Preparation method of hybrid particle toughened epoxy resin composite material | |
| CN105504803B (en) | A kind of high fluidity fiber reinforced nylon composite material and preparation method thereof | |
| CN102775786A (en) | Graphene oxide/cyanate ester composite material and preparation method thereof | |
| CN103525006B (en) | A kind of nanometer SiO2The preparation method of modified glass-fiber/epoxy resin composite material | |
| CN105778424A (en) | Carbon nanotube and carbon fiber synergistically modified epoxy resin composite material and preparation method thereof | |
| CN102190858A (en) | Epoxy resin material toughened by nanometer silica and preparation method thereof | |
| CN105199640A (en) | Method for improving mechanical properties of epoxy resin adhesive by using activated calcium carbonate whisker | |
| CN103242793B (en) | Toughened single-component epoxy resin | |
| CN101885901A (en) | Biphenyl-structure-contained epoxy resin/montmorillonite nano composite material | |
| CN103408927B (en) | Composite fibre modified nylon materials and preparation method thereof | |
| CN100519154C (en) | Mehtod for preparing composite material contg. nano-silicon dioxide, polyurethane and cyanate resin | |
| CN106867202A (en) | A kind of composition epoxy resin | |
| CN104226890B (en) | The waterglass reinforcing agent of casting and preparation method | |
| CN104119642A (en) | Hydantoin epoxy resin modified by nano nitrile rubber and production method of hydantoin epoxy resin | |
| CN101838439A (en) | Nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin and production method thereof | |
| CN114316870B (en) | Injection type bar planting adhesive and preparation method thereof | |
| CN102952374A (en) | Modified thermosetting ultrahigh-molecular epoxy resin composite material | |
| CN113004655A (en) | Preparation method of glass fiber reinforced thermosetting resin prepreg | |
| CN101838438A (en) | Nanometer butadiene-styrene-vinyl pyridine rubber modified epoxy resin and production method thereof | |
| CN108753225A (en) | A kind of room temperature curing metal repairing agent and preparation method thereof | |
| CN104045975B (en) | Preparation method of particle reinforced and toughened resin based fibrous composite material | |
| CN109385045B (en) | Medium-temperature cured high-toughness epoxy resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141029 |