CN1597775A - Preparation technology for composite of epoxy resin nano silicon dioxide - Google Patents
Preparation technology for composite of epoxy resin nano silicon dioxide Download PDFInfo
- Publication number
- CN1597775A CN1597775A CN 200410060769 CN200410060769A CN1597775A CN 1597775 A CN1597775 A CN 1597775A CN 200410060769 CN200410060769 CN 200410060769 CN 200410060769 A CN200410060769 A CN 200410060769A CN 1597775 A CN1597775 A CN 1597775A
- Authority
- CN
- China
- Prior art keywords
- silicon dioxide
- epoxy
- composite material
- nano silicon
- preparation technology
- 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.)
- Granted
Links
Images
Abstract
The invention is a preparing process of epoxy resin nano-SiO2 composite, under the action of ultrasonic wave, adding nano-SiO2 particles to the mixed solutin of silane coupling agent and epoxy active diluter for uniformly mixing, mixing with epoxy resin uniformly by high speed dispersion, then adding in water-borne amine hardener, making low-speed dispersion and curing, pouring the mixture into a mould: constant-temperature and constant-humidity curing for 14 days at T=23plus or minus 2 deg.C and RH= 55 plus or minus 5%, and obtaining it. The nano-SiO2 particles need no surface preprocessing but are directly added to the silane coupling agent-epoxy resin system, thus simplifying the operating procedures of complicated nano-particle surface preprocessing, drying, etc, and improving various properties of epoxy resin composite, beneficial to product industrialization.
Description
Technical field
The present invention relates to a kind of preparation technology of epoxy resin composite material, more particularly it is a kind of preparation technology who adds nano-silicon dioxide particle modified epoxy resin composite material.Matrix material with this prepared has good physical and mechanical property, thermal property and weather resistance; Be applicable in Hydraulic and Hydro-Power Engineering as impact-resisting wear-resisting material, anti-cavitation erosion material, concrete sheath coat material, chemical grouting material etc.
Background technology
Resins, epoxy has mechanical property, dielectric properties and outstanding cementability preferably, has obtained using widely as matrices of composite material, coating, electrically insulating material, tackiness agent etc., is in dominant position in thermosetting resin.In water conservancy project material Application Areas,, thereby application is very widely arranged also in hydro project because of these performances of Resins, epoxy have satisfied some particular requirements of water conservancy project material to a certain extent.As being used as impact-resisting wear-resisting material, anti-cavitation erosion material, concrete sheath coat material, chemical grouting material etc.But it is, more and more higher to the technical requirements of Resins, epoxy along with the growth requirement that the expansion and the water conservancy project of Resins, epoxy Application Areas are built.On the one hand, people wish improving the Resins, epoxy flexible simultaneously, and mechanical property and resistance toheat also are improved simultaneously.
At present, abroad (Japan and the United States, Europe etc.) extensively adopt modifying epoxy resin by organosilicon, promptly blend, copolymerization or the graft reaction by between the two reaches and can reduce the Resins, epoxy internal stress to form intramolecularly again toughness reinforcing, improve resistance to elevated temperatures, also improve organosilyl waterproof, grease proofing, antioxygen property simultaneously.But its set time that needs long (several hrs was by several days), accelerate curing reaction, need be in the usage quantity of comparatively high temps (60 ℃ more than-100 ℃) or increase solidifying agent, this not only increases cost, but also is difficult to satisfy the requirement (time short, room temperature encapsulation) of extensive device production line to packaged material.In addition, in existing method of modifying,, the strength of materials, rigidity are descended if adopt rubber-toughened epoxy resin; If adopt filler to strengthen, toughness can descend again.
The surperficial non-matching atom of nano material is many, and is big with Resins, epoxy generation physics or chemically combined possibility, can strengthen particle and combine with the interface of matrix, and bear certain load, has to strengthen toughness reinforcing possibility.Organic and inorganic nano composite material are exactly to interact mutually with second and the material that forms with nano-scale particle, normally mineral filler is dispersed in the organic polymer skeleton, interact with its big surface-area and framework material, reduce the motility of polymer bonds, this interaction has improved toughness and other mechanical propertys of nanocomposite.Aging (weathering resistance) of otherwise address Resins, epoxy is also particularly important, advanced organic-inorganic epoxide resin nano matrix material, by the dispersion of meticulous control ultrafine inorganic particle in Resins, epoxy and compound, can be with inorganic particulate volume content seldom, in a sizable scope, improve the over-all properties of matrix material effectively, strengthen, toughness reinforcing, anti-aging, and do not influence the processing characteristics of material.
Have to studies confirm that an amount of clay nano particle intensity of reinforced epoxy significantly, improve the Young's modulus of matrix.Nano combined technology of preparing has been widened the Application Areas of Resins, epoxy greatly, and state, inside and outside many R﹠D institutions have carried out the research of this respect in recent years.
Traditional epoxide resin nano silicon dioxide composite material preparation technology at first uses dispersion agent to nanometer SiO
2Modification is carried out on the surface, more under external force the good nanometer SiO of modification
2Be distributed in the Resins, epoxy, because nanometer SiO
2The surface at first needs modification, so its complex process; How to solve the homodisperse problem of nano particle in epoxy resin-base, aging (weathering resistance) problem of Resins, epoxy in addition, improve preparation level and preparation efficiency, still remain further to be studied.Simultaneously, the applied research of nano-material modified Resins, epoxy aspect water conservancy project still is a blank.
Summary of the invention
The objective of the invention is to overcome the weak point of above-mentioned background technology and a kind of epoxide resin nano silicon dioxide composite material preparation technology is provided; Nano-silicon dioxide particle of the present invention need not surface preparation, but directly join in the system of silane coupling agent and Resins, epoxy, schedule of operation such as the nanoparticle surface preparation of complexity in the traditional method, drying have been simplified, improve the various performances of epoxy resin composite material simultaneously, helped the industrialization of product.
The objective of the invention is to reach by following measure: epoxide resin nano silicon dioxide composite material preparation technology is: under action of ultrasonic waves, the nano-silicon dioxide particle of 0.1-5.0 weight part is joined in the mixing solutions of epoxy active diluent of the silane coupling agent of 2-8 weight part and 10-60 weight part and mix, under the rate of dispersion effect of 5000-6000r/min, mix, disperse 40min with the 95-105 parts by weight of epoxy resin; The water-based amine hardener that adds the 40-60 weight part then mixes under the rate of dispersion effect of 100-200r/min again, behind the slaking 15-30min, mixture is poured in the mould; In T=23 ± 2 ℃, under RH=55 ± 5% condition, fixed temperature and humidity solidifies 14d, promptly gets the epoxide resin nano silicon dioxide composite material.
At epoxy active diluent described in the technique scheme is in epoxy propane butyl ether, hexylene glycol glycidyl ether, polyglycidyl ether or the like one or more.
At the amine hardener of water-based described in the technique scheme is the aliphatics modified amine curing agent.
At silane coupling agent described in the technique scheme is in vinyltriethoxysilane, anilinomethyl triethoxysilane, Y propyl group trimethoxy silane, r aminopropyl triethoxysilane or the like one or more.
At mould described in the technique scheme is that tetrafluoroethylene is the mould that material makes, and the tetrafluoroethylene mould is easy to the demoulding.
At nano-silicon dioxide particle described in the technique scheme is that 3.0 weight parts, Resins, epoxy are 100 weight parts.
The application of above-mentioned epoxide resin nano silicon dioxide composite material in preparation water conservancy project material.
Epoxide resin nano silicon-dioxide (the SiO of the present invention's preparation
2) matrix material has good mechanical property, thermal characteristics and weathering resistance.When the nanoparticle consumption reach 3.0 weight parts, when Resins, epoxy is 100 weight parts, it is best that the mechanical property of epoxy resin composite material reaches, shock strength improves 66%, tensile strength improves 52%, elongation at break improves 9%; Nanometer SiO
2The adding of particle has improved the thermostability of epoxy systems, has reduced the second-order transition temperature of epoxy-resin systems, and makes the glass transition zone Tg of nanometer/epoxy composite material broaden, thereby has improved the snappiness of material; The adding of nanoparticle makes the accelerated deterioration time of epoxide resin material bring up to 700 hours from 250 hours.Result of study also shows, when the epoxy resin composite material matrix is subjected to impacting, produces tiny crack (crazing) between particle and the matrix; Matrix between the particle also produces viscous deformation simultaneously, absorbs striking energy, strengthens toughness reinforcing effect thereby reached.Adopt silane coupling agent that nanoparticle is carried out surface treatment in addition, improved Resins, epoxy and nanometer SiO
2Interface binding power has increased SiO
2Dispersiveness and the dispersion stabilization of particle in matrix, the consistency of raising nanoparticle and polymkeric substance makes matrix material mix more evenly.Nanometer SiO
2The median size of particle is 43.83nm (as shown in Figure 2), and the median size that is distributed to Resins, epoxy is 49.61nm (as shown in Figure 3).
Description of drawings
Fig. 1 is the SEM figure of the embodiment of the invention 1 resulting modified resin;
The nanometer SiO that Fig. 2 uses for the present invention
2The initial grain-size graph of particle;
Fig. 3 is that the embodiment of the invention 5 is handled back nanometer SiO
2The grain-size graph of particle.
Embodiment
The inventor finds the simplification technology of preparation epoxide resin nano silicon dioxide composite material finally through studying repeatedly and verifying repeatedly by a large amount of experiments.Describe performance of the present invention in detail below in conjunction with several representative embodiment, but following embodiment is not construed as limiting the invention.
Under the situation of high speed dispersion (5000-6000r/min), with the nano silicon (SiO of 0.1-5.0 weight part
2) particle directly is added in the liquid-state epoxy resin of 95-105 weight part high speed dispersion 40min; The water-based amine hardener that adds the 40-60 weight part then, (100-200r/min) mixes at a slow speed, behind the slaking 20min, mixture is poured in the mould that tetrafluoroethylene makes, (T=23 ± 2 ℃ after fixed temperature and humidity solidifies 14d, RH=55 ± 5%), the polymeric film that obtains is used for various performance tests.
Embodiment 2
Under action of ultrasonic waves, nanoparticle directly is scattered in the liquid-state epoxy resin.Other are with method one.
Embodiment 3
Under action of ultrasonic waves, nano-silicon dioxide particle is scattered in earlier in the epoxy active diluent of 10-60 weight part, and then mixes with Resins, epoxy under the effect of high speed dispersor.Other are with method one.
Embodiment 4
Under the effect of high speed dispersor, earlier the silane coupling agent of 2-8 weight part and the epoxy active diluent of 10-60 weight part are mixed, add nano-silicon dioxide particle then, high speed dispersion 40min, and then under the effect of high speed dispersor, mix with Resins, epoxy.Other are with method one.
Embodiment 5
Under action of ultrasonic waves, the nano-silicon dioxide particle of 0.1-5.0 weight part is joined in the mixing solutions of epoxy active diluent of the silane coupling agent of 2-8 weight part and 10-60 weight part and mix, and then under the effect of high speed dispersor, mix with Resins, epoxy.Other are with method one.
The epoxide resin nano silicon dioxide composite material preparation method that the present invention adopts is embodiment 5, and conclusion is as follows after tested:
(1) in the embodiment 1 resulting modified epoxy the not coacervate of scattered nano-silicon dioxide particle is arranged.
(2) nanometer SiO in the embodiment 2 resulting matrix materials
2Particle disperses more even, effect ratio method one is much better, but there is a little cavity to exist in the material, show that ultrasonic vibration can solve the conglomeration problem of nanoparticle effectively, but then, owing to exist compatibility problem between nanoparticle and the Resins, epoxy, thereby influenced performance of composites (seeing Table 1).
(3) matrix material of embodiment 3 gained because the viscosity of epoxy active diluent is low, so surpass under the situation of 10min in ultrasonic wave action time, nanoparticle just can homodisperse therein.But the nanoparticle after disperseing mixes the performance still relatively poor (seeing Table 1) of the obtained material in back with Resins, epoxy under the effect of high speed dispersor.
(4) matrix material that makes of embodiment 4, test-results shows, though the viscosity of dispersion system has reduced, only under the effect of high speed dispersor, still is difficult to nanometer SiO
2Particle evenly spreads in the low-viscosity epoxy reactive thinner system.The SEM photo of gained material such as embodiment's 1 is similar substantially, but the silane coupling agent that adds in present method increases the consistency that exists between nanoparticle and the Resins, epoxy to a certain extent, thereby the mechanical property of gained matrix material has had raising to a certain degree (seeing Table 1) than the mechanical property of embodiment 1 gained material.So only the tearing by high speed dispersor is to be difficult to nanometer SiO with the effect of peeling off
2Particle is dispersed into simple particle.
(5) embodiment 5, and test-results shows, surpasses under the condition of 10min in the action of ultrasonic waves time, just can be with nanometer SiO
2Particle evenly spreads in the mixing solutions of silane coupling agent and epoxy active diluent.Fig. 2 is the nanometer SiO that adopts the Ma Erwen particle size analyzer determination
2The initial particle diameter of particle, Fig. 3 are the nanometer SiO in the system that records after adopting present method to disperse
2The particle diameter of particle.Comparison diagram 2 and Fig. 3 adopt the embodiment 5 can be with nanometer SiO as can be seen
2Particle is dispersed into simple nanoparticle, but nano particle diameter and dispersion index after handling all have less increase, and this causes owing to silane coupling agent is adsorbed on nanoparticle surface.
The different preparation methods of table 1 to the influence of composite materials property
Shock strength (kJ.m
-2) 9.6 13.0 11.6 13.5 15.0
Tensile strength (MPa) 35.2 44.6 43.3 45.0 49.6
Elongation at break (%) 18.3 19.0 18.6 19.2 19.8
As known from Table 1: the mechanics performance determining result of material also shows mechanical property the best of embodiment 5 prepared materials.
The high speed dispersor of Cai Yonging is that Shanghai Modern Environmental Engineering Technology Co., Ltd. produces in the above-described embodiment.Model is GFJ-0.4, and speed adjustable range is: 0-8000r/min.Also can adopt the equipment of other manufacturer.
Need to prove: to those of ordinary skill in the art, can also make some changes or distortion to the present invention under the prerequisite that does not change the principle of the invention, this belongs to protection scope of the present invention equally.
Claims (7)
1, epoxide resin nano silicon dioxide composite material preparation technology, it is characterized in that described preparation technology is: under action of ultrasonic waves, the nano-silicon dioxide particle of 0.1-5.0 weight part is joined in the mixing solutions of epoxy active diluent of the silane coupling agent of 2-8 weight part and 10-60 weight part and mix, under the rate of dispersion effect of 5000-6000r/min, mix, disperse 40min with the 95-105 parts by weight of epoxy resin; The water-based amine hardener that adds the 40-60 weight part then mixes under the rate of dispersion effect of 100-200r/min again, behind the slaking 15-30min, mixture is poured in the mould; In T=23 ± 2 ℃, under RH=55 ± 5% condition, fixed temperature and humidity solidifies 14d, promptly gets the epoxide resin nano silicon dioxide composite material.
2, epoxide resin nano silicon dioxide composite material preparation technology according to claim 1 is characterized in that described epoxy active diluent is one or more in epoxy propane butyl ether, hexylene glycol glycidyl ether, the polyglycidyl ether.
3, epoxide resin nano silicon dioxide composite material preparation technology according to claim 1 is characterized in that described water-based amine hardener is the aliphatics modified amine.
4, epoxide resin nano silicon dioxide composite material preparation technology according to claim 1 is characterized in that described silane coupling agent is one or more in vinyltriethoxysilane, anilinomethyl triethoxysilane, Y propyl group trimethoxy silane, the r aminopropyl triethoxysilane.
5, epoxide resin nano silicon dioxide composite material preparation technology according to claim 1 is characterized in that described mould is that tetrafluoroethylene is the mould that material makes.
6, epoxide resin nano silicon dioxide composite material preparation technology according to claim 1 is characterized in that described nano-silicon dioxide particle is that 3.0 weight parts, Resins, epoxy are 100 weight parts.
7, the application of epoxide resin nano silicon dioxide composite material is characterized in that the application of described matrix material in preparation water conservancy project material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410060769 CN1256373C (en) | 2004-08-26 | 2004-08-26 | Preparation technology for composite of epoxy resin nano silicon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410060769 CN1256373C (en) | 2004-08-26 | 2004-08-26 | Preparation technology for composite of epoxy resin nano silicon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597775A true CN1597775A (en) | 2005-03-23 |
| CN1256373C CN1256373C (en) | 2006-05-17 |
Family
ID=34666330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410060769 Expired - Fee Related CN1256373C (en) | 2004-08-26 | 2004-08-26 | Preparation technology for composite of epoxy resin nano silicon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1256373C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584109A (en) * | 2012-01-13 | 2012-07-18 | 雷运波 | Epoxy resin concrete material and microwave-coagulation preparation method thereof |
| CN103113697A (en) * | 2013-03-11 | 2013-05-22 | 中山大学 | Creep-resistant inorganic nano-particle/polymer composite material and preparation method thereof |
| CN103113712A (en) * | 2013-02-04 | 2013-05-22 | 佛山市科富科技有限公司 | Preparation method and application of modified nano-silicon dioxide toughened epoxy resin |
| CN103421277A (en) * | 2013-07-25 | 2013-12-04 | 太原理工大学 | Preparation method of epoxy composite material on basis of nano silica particles |
| CN104530647A (en) * | 2014-12-25 | 2015-04-22 | 太原理工大学 | Method for preparing epoxy resin/nanometer silicon oxide composite material by centrifugation-assisted method |
| CN104672785A (en) * | 2014-06-30 | 2015-06-03 | 广东丹邦科技有限公司 | Epoxy molding compound and preparation method thereof |
| CN105601982A (en) * | 2016-02-04 | 2016-05-25 | 中南大学 | Preparation method of nano silicon dioxide-epoxy resin porous composite material |
| CN107915426A (en) * | 2017-12-04 | 2018-04-17 | 湖南辰砾新材料有限公司 | A kind of high performance grouting material based on silicon dioxide microsphere and preparation method thereof |
| CN108753100A (en) * | 2018-05-03 | 2018-11-06 | 东南大学 | A kind of water-base epoxy concrete repair interfacial agents and preparation method thereof |
| CN111701831A (en) * | 2020-07-03 | 2020-09-25 | 合肥学院 | Preparation method of hydrophobic silica nanoparticle modified epoxy resin anticorrosive film coated on carbon steel |
| CN113563693A (en) * | 2021-06-25 | 2021-10-29 | 中科院广州化学有限公司 | Liquid crystal epoxy resin-mesoporous silica composite material, preparation method and application |
| CN115073211A (en) * | 2022-06-27 | 2022-09-20 | 浙江大学杭州国际科创中心 | Nano-enhanced penetration hardening agent and preparation method thereof |
| CN115637021A (en) * | 2022-10-17 | 2023-01-24 | 华中科技大学 | Modified silicon dioxide synergistically dispersed epoxy resin composite material and preparation and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100567393C (en) * | 2008-03-20 | 2009-12-09 | 江南大学 | A kind of surface modified spherical SiO 2The preparation method of particulate epoxy resin composite material |
| KR102614121B1 (en) * | 2016-11-24 | 2023-12-14 | 현대자동차주식회사 | Clutch |
-
2004
- 2004-08-26 CN CN 200410060769 patent/CN1256373C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584109A (en) * | 2012-01-13 | 2012-07-18 | 雷运波 | Epoxy resin concrete material and microwave-coagulation preparation method thereof |
| CN103113712A (en) * | 2013-02-04 | 2013-05-22 | 佛山市科富科技有限公司 | Preparation method and application of modified nano-silicon dioxide toughened epoxy resin |
| CN103113712B (en) * | 2013-02-04 | 2015-04-01 | 广东科富科技股份有限公司 | Preparation method and application of modified nano-silicon dioxide toughened epoxy resin |
| CN103113697A (en) * | 2013-03-11 | 2013-05-22 | 中山大学 | Creep-resistant inorganic nano-particle/polymer composite material and preparation method thereof |
| CN103113697B (en) * | 2013-03-11 | 2015-05-27 | 中山大学 | Creep-resistant inorganic nano-particle/polymer composite material and preparation method thereof |
| CN103421277A (en) * | 2013-07-25 | 2013-12-04 | 太原理工大学 | Preparation method of epoxy composite material on basis of nano silica particles |
| CN103421277B (en) * | 2013-07-25 | 2015-09-09 | 太原理工大学 | Based on the preparation method of the epoxy resin composite material of nano oxidized silicon grain |
| CN104672785B (en) * | 2014-06-30 | 2019-04-09 | 广东丹邦科技有限公司 | A kind of epoxy-plastic packaging material and preparation method thereof |
| CN104672785A (en) * | 2014-06-30 | 2015-06-03 | 广东丹邦科技有限公司 | Epoxy molding compound and preparation method thereof |
| CN104530647A (en) * | 2014-12-25 | 2015-04-22 | 太原理工大学 | Method for preparing epoxy resin/nanometer silicon oxide composite material by centrifugation-assisted method |
| CN105601982A (en) * | 2016-02-04 | 2016-05-25 | 中南大学 | Preparation method of nano silicon dioxide-epoxy resin porous composite material |
| CN107915426A (en) * | 2017-12-04 | 2018-04-17 | 湖南辰砾新材料有限公司 | A kind of high performance grouting material based on silicon dioxide microsphere and preparation method thereof |
| CN108753100A (en) * | 2018-05-03 | 2018-11-06 | 东南大学 | A kind of water-base epoxy concrete repair interfacial agents and preparation method thereof |
| CN108753100B (en) * | 2018-05-03 | 2020-05-05 | 东南大学 | Water-based epoxy concrete repairing interface agent and preparation method thereof |
| CN111701831A (en) * | 2020-07-03 | 2020-09-25 | 合肥学院 | Preparation method of hydrophobic silica nanoparticle modified epoxy resin anticorrosive film coated on carbon steel |
| CN113563693A (en) * | 2021-06-25 | 2021-10-29 | 中科院广州化学有限公司 | Liquid crystal epoxy resin-mesoporous silica composite material, preparation method and application |
| CN113563693B (en) * | 2021-06-25 | 2024-03-29 | 中科院广州化学有限公司 | Liquid crystal epoxy resin-mesoporous silica composite material, preparation method and application |
| CN115073211A (en) * | 2022-06-27 | 2022-09-20 | 浙江大学杭州国际科创中心 | Nano-enhanced penetration hardening agent and preparation method thereof |
| CN115073211B (en) * | 2022-06-27 | 2023-05-23 | 浙江大学杭州国际科创中心 | Nanometer enhanced penetration hardening agent and preparation method thereof |
| CN115637021A (en) * | 2022-10-17 | 2023-01-24 | 华中科技大学 | Modified silicon dioxide synergistically dispersed epoxy resin composite material and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1256373C (en) | 2006-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1256373C (en) | Preparation technology for composite of epoxy resin nano silicon dioxide | |
| CN107674622B (en) | High-performance structural adhesive for water environment reinforcing engineering and preparation method thereof | |
| CN108559431B (en) | Interface adhesive for bonding new and old concrete and preparation method and construction process thereof | |
| CN1288206C (en) | Epoxy resin/montmorillonoid nano-compoiste-material and its preparation method | |
| CN110982482B (en) | Low-modulus high-elongation silicone sealant with good adhesion and preparation method thereof | |
| CN112079593B (en) | Siloxane modified super-hydrophobic geopolymer anticorrosive material and preparation method thereof | |
| CN114752329B (en) | High-temperature-resistant and cracking-free epoxy color sand joint beautifying agent and preparation method thereof | |
| CN102276764A (en) | Chemical modification method of polymer powder | |
| CN100567393C (en) | A kind of surface modified spherical SiO 2The preparation method of particulate epoxy resin composite material | |
| CN101597436B (en) | Silicon tiny powder surface treating and modifying method, epoxy resin combination and preparation method thereof | |
| CN111718680A (en) | Interface adhesive for improving bonding force of new and old concrete and preparation method and construction process thereof | |
| CN1234796C (en) | Epoxy modified organic silicon resin adhesive | |
| CN108275913A (en) | A kind of bridge epoxy resin mortar and preparation method thereof | |
| CN109135460A (en) | A kind of high strength and waterproof polymer emulsion building water-proof paint and preparation method thereof | |
| CN101457011A (en) | Preparation of composite nano particle modified epoxy resin | |
| CN104327493A (en) | Preparation method of nanometer SiO2 modified PVA-EP-PU interpenetrating polymer network composite material | |
| CN107746550B (en) | High-permeability non-shrinkage epoxy grouting material | |
| CN113897160A (en) | Carbon fiber cloth adhesive for underwater or humid environment reinforcement engineering and preparation method thereof | |
| CN1118508C (en) | Organic silicon/epoxy resin packing material modified with nanometer-level silicon-base oxide | |
| CN1238459C (en) | High connecting intensity thermosetting conducting resin | |
| KR102160724B1 (en) | Silicon crack repairing agent and manufacturing method thereof and crack repairing method for concrete structure using thereof | |
| CN105802488A (en) | Coating containing composite silicone rubber and preparation method of coating | |
| CN114316870B (en) | Injection type bar planting adhesive and preparation method thereof | |
| CN105778420B (en) | A kind of epoxy resin-base composite material and preparation method thereof | |
| CN113955985A (en) | Dry-mixed mortar and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060517 Termination date: 20110826 |