CN103265926A - Composite nano powder modified imine epoxy adhesive - Google Patents
Composite nano powder modified imine epoxy adhesive Download PDFInfo
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- CN103265926A CN103265926A CN2013102190063A CN201310219006A CN103265926A CN 103265926 A CN103265926 A CN 103265926A CN 2013102190063 A CN2013102190063 A CN 2013102190063A CN 201310219006 A CN201310219006 A CN 201310219006A CN 103265926 A CN103265926 A CN 103265926A
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Abstract
The invention discloses a composite nano powder modified imine epoxy adhesive. The composite nano powder modified imine epoxy adhesive is prepared by mixing mixed nano powder and an imine epoxy adhesive through a direct doping method, and the shear strength of the imine epoxy adhesive at room temperature is greatly improved, reaches 35MPa and is improved by about 35 percent compared with the imine epoxy adhesive without containing the nano powder. The high-temperature resistance of the imine epoxy adhesive added with the nano powder is also greatly improved. Meanwhile, by adopting the direct doping method, the preparation method is simple and easy to operate.
Description
Technical field
The present invention relates to a kind of sizing agent, particularly a kind of imines epoxy adhesive of composite nano powder modification.
Background technology
The agent of Resins, epoxy gluing claims epoxy adhesive again, be called for short epoxy glue, since beginning to use the 1950's, development is very fast, be performance comparatively comprehensively, use a class sizing agent quite widely, in synthetic adhesive, no matter be performance and kind, or purposes and value, epoxy adhesive all occupies critical role, is the outstanding person in the structural adhesive.Epoxy adhesive because of its cohesive strength height, cure shrinkage is low, creep resistance is strong, dimensional stability is good, resistant to chemical media, advantages such as electrical insulation capability is good, physical strength is high, good processability, is widely used in each field such as aerospace, defence and military, electronics, machinery, building, light industry.Development of high-tech is maked rapid progress at present, the epoxy adhesive kind is constantly weeded out the old and bring forth the new, and the exploitation of high-performance epoxy resin, novel solidifying agent, good toughner, nano material, environmental protection fire retarding agent etc. has promoted competitive capacity and the application prospect of epoxy adhesive more comprehensively, excellent comprehensive performance and wide application field, make epoxy adhesive in modern tackiness agent, come out top, have huge development potentiality.In recent years, epoxy adhesive just develops towards high strength, high tenacity, high heat-resisting, high durable, multi-functional, flame retardant type, environmental protection direction.
Epoxy adhesive can replace welding, riveted joint, the bolt of mechanical traditional technology to connect, and has an extensive use in the reinforcing maintenance of aviation, automobile, light industry and machinery manufacturing, electronics, buildings, the fields such as repairing on highway airport.Why the agent of Resins, epoxy gluing is subjected to people is paid attention to, and is because it has lot of advantages:
(1) extensive bonding various material.Epoxy adhesive is widely used in the bonding of various metals, to the glass in the non-metallic material, cement products, stone material, timber, fabric, porcelain etc., all can carry out bonding; Even rubber, plastics also have good bonding strength; For very difficult bonding polyolefins plastics, as long as its surface is suitably handled, also can reach than high-adhesive-strength;
(2) bonding force is strong, physical strength is high.Contain aliphatics in the epoxy adhesive molecular chain through base, ether, its strong polarity make Resins, epoxy with produced Van der Waals force by bonding interface, so have very high bonding strength;
(3) shrinkability is low.The reaction of Resins, epoxy and solidifying agent is the ring-opening polymerization of direct addition reaction or epoxy group(ing), does not have water or other volatile byproducts to generate therebetween, so shrinking percentage is very low; Resins, epoxy is a class (less than 2%) of shrinking percentage minimum in the thermosetting resin, if add filler, the shrinking percentage of Resins, epoxy can lower (/ 0.1%);
(4) electrical insulation capability is superior.Epoxy-resin systems after the curing is a kind of superior isolation material with high dielectric property, anti-surface leakage, anti-electric arc;
(5) chemical stability.Resins, epoxy contains phenyl ring, ehter bond, solidifies the back compact structure, so have good alkali resistance, acid resistance and solvent resistance;
(6) anti-mould.The anti-most of moulds of Resins, epoxy of solidifying can be used under the tropicalization of harshness.
Though many advantages are arranged, from making to see that still there is following problem in epoxy adhesive:
(1) cured article of tackiness agent when not toughness reinforcing is general crisp partially, and snappiness is poor, causes the application in machinery manufacturing industry to be subjected to bigger restriction; Its temperature tolerance is also relatively poor simultaneously, generally only can be at life-time service below 150 ℃;
(2) some starting material such as reactive thinner, solidifying agent etc. have in various degree toxicity and pungency, should avoid selecting for use during component design as far as possible, should add forced ventilation and protection during constructing operation.
Over year, adopt nano-inorganic substance very active to the research that polymkeric substance carries out modification surplus in the of nearly ten.Because the size of nanoparticle is very little, specific surface area is very big, its surface effects, volume effect, quantum size effect and macro quanta tunnel effect are remarkable, make Organic present many conventional polymer properties of materials that are different from.There are some researches show, introduce nano inorganic powder after, can improve normal temperature, the mechanical behavior under high temperature (as the shearing resistance of sizing agent) of sizing agent significantly, to the second-order transition temperature of sizing agent, apparent decomposition temperature has that certain influence is also arranged.
Summary of the invention
The objective of the invention is to overcome the defective that existing epoxy adhesive exists, provide a kind of mechanical property good, resistant to elevated temperatures epoxy adhesive.
In order to realize above goal of the invention, the present invention by the following technical solutions: a kind of composite nano powder modification imines epoxy adhesive comprises the component of following mass fraction: 100 parts of Resins, epoxy; 30～40 parts of terminal hydroxy group imine intermediate; 5～20 parts of nano silicons; 5～20 parts of nano titanium oxides; 5～20 parts of nano aluminium oxides; 30～40 parts of solvents; 10～15 parts of toughner; 20～30 parts in solidifying agent.
Described Resins, epoxy is a kind of in bisphenol A-type, Bisphenol F type or the ethylene oxidic ester epoxy resin.
Described nano silicon particle diameter is 20～50nm.
Described nano titanium oxide particle diameter is 20～50nm.
Described nano aluminium oxide particle diameter is 20～50nm.
Described solvent is the mixed solvent of dioxane, toluene and DDS.
Described toughner is DBP.
Described solidifying agent is T-31.
Nano material is because size is far smaller than common material, therefore show the not available nano effect of a lot of common materials, nano material has unique characteristics such as surface effects, small-size effect and macro quanta tunnel effect because size is little, and specific surface area is big, surface energy is high.Naous W etc. has prepared Resins, epoxy/A1 with blending method
2O
3Nano composite material is discovered nanometer A1
2O
3Particle can be when improving Resins, epoxy toughness and do not damage its intensity and thermotolerance.Usefulness nano imvite K-10 such as Zhou Y X come modification SC-15DGEBA epoxy resin-base composite material, and the adding of K-10 increases the tensile modulus of system and tensile strength, the flexible reduction.Chen Z K etc. are with the low temperature mechanical property of multi-walled carbon nano-tubes modified epoxy, the result show system over-all properties be improved significantly, expanded the application of epoxy glue in the cryogenic engineering field.Mirm " ABS/ nano imvite/nano-TiO such as hseni A
2Modified synergic Resins, epoxy also greatly reduces the modification cost when enhancing is toughness reinforcing.
Major advantage of the present invention and beneficial effect are: adopt direct doping method, nano silicon, nano titanium oxide, nano aluminium oxide all can be compound preferably with the imines epoxy adhesive.Shearing resistance under the imines epoxy adhesive room temperature has had raising largely, and the shearing resistance under the room temperature reaches 35MPa, has improved about 35% than the shearing resistance under the imines epoxy adhesive room temperature that does not contain nano-powder.Imines epoxy adhesive resistance to elevated temperatures behind the adding nano-powder also is greatly increased.Adopt direct doping method simultaneously, the simple easy handling of preparation method.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment one:
Prepare raw material by following mass fraction: 100 parts of bisphenol f type epoxy resins; 35 parts of terminal hydroxy group imine intermediate; 10 parts of nano silicons; 10 parts of nano titanium oxides; 10 parts of nano aluminium oxides; 30 parts of the mixed solvents of dioxane, toluene and DDS; Toughner DBP10 part; 25 parts of solidifying agent T-31;
Resins, epoxy is warming up to 130 ℃ and stirs, and adds the terminal hydroxy group imines, is warming up to 160 ℃ after the stirring, gets imine modified Resins, epoxy;
In imine modified Resins, epoxy, add solvent, at 120 ℃ of stirring and refluxing 3h, be cooled to 50 ℃, add nano silicon, nano titanium oxide and nano aluminium oxide high speed dispersion 30min, add toughner and solidifying agent, stir and namely get composite nano powder modification imines epoxy adhesive.
Embodiment two:
Prepare raw material by following mass fraction: 100 parts of ethylene oxidic ester epoxy resins; 30 parts of terminal hydroxy group imine intermediate; 5 parts of nano silicons; 15 parts of nano titanium oxides; 20 parts of nano aluminium oxides; 40 parts of the mixed solvents of dioxane, toluene and DDS; Toughner DBP15 part; 30 parts of solidifying agent T-31;
Resins, epoxy is warming up to 130 ℃ and stirs, and adds the terminal hydroxy group imines, is warming up to 160 ℃ after the stirring, gets imine modified Resins, epoxy;
In imine modified Resins, epoxy, add solvent, at 120 ℃ of stirring and refluxing 3h, be cooled to 50 ℃, add nano silicon, nano titanium oxide and nano aluminium oxide high speed dispersion 30min, add toughner and solidifying agent, stir and namely get composite nano powder modification imines epoxy adhesive.
Embodiment three:
Prepare raw material by following mass fraction: 100 parts of bisphenol A type epoxy resins; 40 parts of terminal hydroxy group imine intermediate; 20 parts of nano silicons; 5 parts of nano titanium oxides; 5 parts of nano aluminium oxides; 35 parts of the mixed solvents of dioxane, toluene and DDS; 12 parts of toughner DBP; 25 parts of solidifying agent T-31;
Resins, epoxy is warming up to 130 ℃ and stirs, and adds the terminal hydroxy group imines, is warming up to 160 ℃ after the stirring, gets imine modified Resins, epoxy;
In imine modified Resins, epoxy, add solvent, at 120 ℃ of stirring and refluxing 3h, be cooled to 50 ℃, add nano silicon, nano titanium oxide and nano aluminium oxide high speed dispersion 30min, add toughner and solidifying agent, stir and namely get composite nano powder modification imines epoxy adhesive.
Embodiment four:
Prepare raw material by following mass fraction: 100 parts of ethylene oxidic ester epoxy resins; 36 parts of terminal hydroxy group imine intermediate; 12 parts of nano silicons; 10 parts of nano titanium oxides; 10 parts of nano aluminium oxides; 36 parts of the mixed solvents of dioxane, toluene and DDS; 14 parts of toughner DBP; 28 parts of solidifying agent T-31;
Resins, epoxy is warming up to 130 ℃ and stirs, and adds the terminal hydroxy group imines, is warming up to 160 ℃ after the stirring, gets imine modified Resins, epoxy;
In imine modified Resins, epoxy, add solvent, at 120 ℃ of stirring and refluxing 3h, be cooled to 50 ℃, add nano silicon, nano titanium oxide and nano aluminium oxide high speed dispersion 30min, add toughner and solidifying agent, stir and namely get composite nano powder modification imines epoxy adhesive.
The thick stainless steel of 3.0mm is adopted in test piece, by the following method surface treatment is carried out in test piece before the applying glue: after rinsing well with No. 100 sand paper sand millings → in 60 ℃ 6% sodium hydroxide solution, soak 10min → with tap water, in 50 ℃ 10% hydrochloric acid soln, soak 10min → rinse the back oven dry well with tap water.Glueing joint face brushing sizing agent twice, every all over drying by following condition behind the brushing sizing agent: 120 ℃ of 0. 5h+140 ℃ 15min of 100 ℃ of 0. 5h+.About 0.08～the 0.12mm of glued membrane total thickness behind the desolventizing.In the fixed mould that glue-coated test piece is stacked in, the adjustment loading pressure is 0.1～0.2MPa, puts into baking oven and solidifies by following condition: 220 ℃ of 2h of 200 ℃ of 2h+ of 180 ℃ of 1h+ of 140 ℃ of 1h+.
Performance test:
(1) cutting performance: with day island proper Tianjin AG-201 of company type electronic type universal material testing machine, press GB/T 7124-1986 sizing agent tensile shear strength measuring method regulation and measure shearing resistance;
(2) resistance to elevated temperatures: measure apparent decomposition temperature with the comprehensive thermal analyzer of the German NETZSCH STA449 of company in air atmosphere, temperature rise rate is 5e/min.
Test result shows: the shearing resistance under the imines epoxy adhesive room temperature has had raising largely, and the shearing resistance under the room temperature reaches 35MPa, has improved about 35% than the shearing resistance under the imines epoxy adhesive room temperature that does not contain nano-powder.Imines epoxy adhesive resistance to elevated temperatures behind the adding nano-powder also is greatly increased.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (8)
1. composite nano powder modification imines epoxy adhesive is characterized in that comprising the component of following mass fraction: 100 parts of Resins, epoxy; 30～40 parts of terminal hydroxy group imine intermediate; 5～20 parts of nano silicons; 5～20 parts of nano titanium oxides; 5～20 parts of nano aluminium oxides; 30～40 parts of solvents; 10～15 parts of toughner; 20～30 parts in solidifying agent.
2. composite nano powder modification imines epoxy adhesive according to claim 1 is characterized in that: described Resins, epoxy is a kind of in bisphenol A-type, Bisphenol F type or the ethylene oxidic ester epoxy resin.
3. composite nano powder modification imines epoxy adhesive according to claim 1, it is characterized in that: described nano silicon particle diameter is 20～50nm.
4. composite nano powder modification imines epoxy adhesive according to claim 1, it is characterized in that: described nano titanium oxide particle diameter is 20～50nm.
5. composite nano powder modification imines epoxy adhesive according to claim 1, it is characterized in that: described nano aluminium oxide particle diameter is 20～50nm.
6. composite nano powder modification imines epoxy adhesive according to claim 1, it is characterized in that: described solvent is the mixed solvent of dioxane, toluene and DDS.
7. composite nano powder modification imines epoxy adhesive according to claim 1, it is characterized in that: described toughner is DBP.
8. composite nano powder modification imines epoxy adhesive according to claim 1, it is characterized in that: described solidifying agent is T-31.
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Cited By (3)
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| CN105176463A (en) * | 2015-08-06 | 2015-12-23 | 安徽铭源新型建材科技有限公司 | Wallboard with good heat-resistant caking property and excellent mechanical property |
| CN105623197A (en) * | 2016-04-08 | 2016-06-01 | 章俊 | Epoxy resin (EP) nano plastic and preparation method thereof |
| CN107936895A (en) * | 2017-12-15 | 2018-04-20 | 马鞍山松鹤信息科技有限公司 | A kind of high-durability gluing thing and its preparation process for light industry bonding |
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| CN107793982A (en) * | 2017-10-26 | 2018-03-13 | 鹤山市怡信化工厂有限公司 | A kind of new Epoxy-imide adhesive and preparation method |
| CN107603547A (en) * | 2017-10-26 | 2018-01-19 | 鹤山市怡信化工厂有限公司 | A kind of nano-material modified Epoxy-imide adhesive |
| CN107722898A (en) * | 2017-10-26 | 2018-02-23 | 鹤山市怡信化工厂有限公司 | A kind of composite nano materials modified imide epoxy adhesive |
| CN107722899A (en) * | 2017-10-26 | 2018-02-23 | 鹤山市怡信化工厂有限公司 | A kind of galapectite modified imide epoxy adhesive and preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176463A (en) * | 2015-08-06 | 2015-12-23 | 安徽铭源新型建材科技有限公司 | Wallboard with good heat-resistant caking property and excellent mechanical property |
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| CN107936895A (en) * | 2017-12-15 | 2018-04-20 | 马鞍山松鹤信息科技有限公司 | A kind of high-durability gluing thing and its preparation process for light industry bonding |
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