CN104119827A - Room-temperature-curing epoxy-acid anhydride adhesive and preparation method thereof - Google Patents
Room-temperature-curing epoxy-acid anhydride adhesive and preparation method thereof Download PDFInfo
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- CN104119827A CN104119827A CN201410359604.5A CN201410359604A CN104119827A CN 104119827 A CN104119827 A CN 104119827A CN 201410359604 A CN201410359604 A CN 201410359604A CN 104119827 A CN104119827 A CN 104119827A
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Abstract
The invention discloses an epoxy-acid anhydride adhesive capable of quickly curing at room temperature (25 DEG C) and a preparation method thereof. The adhesive is composed of an epoxy resin, a sulfhydryl compound, a toughener, an acid anhydride and a filler. By utilizing the high activity of the sulfhydryl group in the sulfhydryl compound, the ring of the epoxy group is opened at lower temperature, thereby lowering the activation energy for the curing reaction of the epoxy-acid anhydride adhesive; and thus, the epoxy-acid anhydride adhesive can be completely cured at 25 DEG C for 48 hours or completely cured at the temperature of higher than 25 DEG C within 48 hours under the condition of not using any curing accelerator. The bonding strength of the epoxy-acid anhydride adhesive is greater than 20 MPa, and thus, the epoxy-acid anhydride adhesive satisfies the conventional bonding and potting demands. The formula system of the epoxy-acid anhydride adhesive does not influence the storage stability of the cured substance; and the method lowers the production cost, avoids the problem of debonding due to expansion caused by heat and contraction caused by cold when the temperature rises and falls in the hot-temperature curing process, and widens the application range of the epoxy-acid anhydride adhesive.
Description
Technical field
The present invention relates to a kind of technical field of epoxy-acid anhydrides tackiness agent, relate in particular to a kind of room-temperature curing epoxy-acid anhydrides tackiness agent.
Background technology
Epoxyn occurs so far only only having more than 60 year from about nineteen fifty.But along with the proposition in succession of the various gluing theories of 20 middle of century, and the deep progress of the basic research work such as tackiness agent chemistry, tackiness agent rheology and gluing failure mechanisms, make Adhensive performance, kind and application have the development of advancing by leaps and bounds.Epoxies tackiness agent is mainly made up of epoxy resin and solidifying agent two parts.Epoxy resin and curing system thereof be also with the continuing to bring out of its uniqueness, excellent performance and neo-epoxy resin, Novel curing agent and additive, and becomes excellent performance, kind is numerous, adaptability the is extensive important tackiness agent of a class.For improving some performance, meet different purposes and can also add the subsidiary material such as toughner, thinner, promotor, coupling agent.Because the bonding strength of epoxy adhesive is high, highly versatile, once there is the title of " multi-purpose adhesive ", " strong adhesive ", be widely used in fields such as Aeronautics and Astronautics, automobile, machinery, building, chemical industry, light industry, electronics, electrical equipment and daily lifes.
Epoxy resin, is called for short EP, because having good mechanical property and electrical insulation capability, excellent adhesiveproperties, the good performance such as performance of technical process and resistance to chemical attack, is widely used in fields such as electric, mechanical, building, space flight and aviation.According to molecular structure, epoxy resin can be divided into glycidyl ether based epoxy resin, glycidyl ester based epoxy resin, Racemic glycidol amine epoxy resin, line style aliphatic category epoxy resin and alicyclic based epoxy resin substantially.Epoxy resin only could be realized its various performances in the time being cured with solidifying agent the cured article that reacts generation cross-linked structure, the curing reaction of epoxy resin is mainly to complete by the ring-opening reaction of epoxy group(ing), and the kind of solidifying agent has considerable influence to the performance of epoxy resin cured product.
Conventional epoxy curing agent has aliphatic amide, aliphatic cyclic amine, aromatic amine, polymeric amide, acid anhydrides, resene, tertiary amine, and under the effect of light trigger, ultraviolet ray or light also can make epoxy resin cure in addition.Normal temperature or low-temperature curing are generally selected amine curing agent, and heating cure is conventional acid anhydrides, aromatics solidifying agent.Conventionally solidify taking amine as main, have the anhydrides of requirement on electric performance for conventional.Compare with amine curing agent, acid anhydride type curing agent has that volatility is little, toxicity is low, working life is long, cure shrinkage is little, thermotolerance and the characteristic such as electrical property is good, comparatively general in the application of large-scale casting and electric industry.
Acid anhydrides open loop under the effect of hydroxyl, minor amount of water and the hydroxy-containing compounds of epoxy resin, the carboxyl and the epoxy group(ing) addition that generate obtain ester group, the hydroxyl that esterification generates and hydroxyl catalysis epoxy addition generation etherification reaction in the time of high temperature of epoxy resin, like this, open loop-ester-etherificate is constantly carried out repeatedly, until cross linking of epoxy resin solidifies, the curing mechanism of Here it is acid anhydrides.
But, acid anhydride type curing agent is because specific activity is lower, self-vulcanizing is slow, curing cycle is longer, need be heating and curing, and generally needs comparatively high temps (being generally more than 100 DEG C) to solidify, therefore be unfavorable for site operation, be not suitable for the bonding and embedding of the material that tolerable temperature is lower, and in temperature-fall period, may produce bonding break-off etc. owing to expanding with heat and contract with cold after being heating and curing and solidifying.These problems have seriously restricted the Application Areas of epoxy-acid anhydrides tackiness agent, for example, in aviation, in machinery and electronic industry, some large-scale or meticulous parts is bonding, embedding, the Rapid-Repair of aircraft breakage, the reparation of historical relic and protection, bonding etc. in moist surface and water, under these occasions, do not wish or do not allow even may not be heating and curing, the effective way solving is epoxy-acid anhydrides tackiness agent that acquisition can be curing under normal temperature or lesser temps, and do not use catalyzer, promotor, in order to avoid the performance that material or tackiness agent are glued in residue impact in use or storage process.
In the past, the research of epoxy-acid anhydrides tackiness agent mainly concentrates on and improves condensate performance, few for the research report that reduces solidification value.He Wendong etc. adopt heat-resisting benzophenone tetracarboxylic dianhydride (BTDA) to solidify four functionality glycidyl amine epoxy resin, make 60 DEG C of curing heat resistant epoxide resins (EP) tackiness agent, its room temperature shearing resistance is 13.91MPa, 150 DEG C of shearing resistances be 10.63MPa (He Wendong etc. preparation and the performance study of 150 DEG C of epoxyns of self-vulcanizing heatproof. Chinese tackiness agent, 2008 (9): 28-30); The aircraft repair sheets of Sun Dongzhou etc. development are at 100 DEG C of curing 3h, normal temperature shearing resistance be 30.6MPa, 175 DEG C of shearing resistances be 12.8MPa (Sun Dongzhou etc. the development of aircraft repair sheets. chemical and bonding, 2003 (6): 286-288); Shi Na etc. are taking 2 ethyl hexanoic acid chromium as catalyzer, realize the self-vulcanizing of epoxy-anhydride system, 25 DEG C solidify 7 days Al/Al and draw that to cut intensity be 6.17MPa, 30 DEG C solidify 7 days Al/Al draw cut intensity be 15.84-20.43MPa (Shi Na etc. the self-vulcanizing performance research of acid anhydrides and epoxy resin. extraordinary chemical materials technical seminar collection of thesis, 2006:91-95).
In sum, at present less to reducing the research of solidification value aspect, the solidification value of epoxy-acid anhydrides tackiness agent of prior art is higher or set time is longer.Self-vulcanizing or at a lower temperature curing epoxy adhesive have obvious superiority in engineering application, reduce solidification value, be conducive to expand the range of application of epoxy-acid anhydrides tackiness agent, there is very important practical value for fields such as electric, space flight and aviation.
Summary of the invention
The object of the invention is to be to provide a kind of preparation method easy, can large-scale production, can at room temperature solidify, and set time shorter epoxy-acid anhydrides tackiness agent.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
The present invention is taking epoxy resin as matrix resin, and acid anhydrides is solidifying agent, and toughner improves tackiness agent snappiness, and filler plays toughness reinforcing enhancement.The present invention utilizes the high reactivity of sulfydryl in sulfhydryl compound, make at a lower temperature epoxy ring-opening, the hydroxyl of generation can with anhydride reaction, thereby reduced the activation energy of reaction.
The present invention proposes a kind of room-temperature curing epoxy-acid anhydrides tackiness agent, and it is to contain following component: in weight part
100 parts of epoxy resin;
Toughner 20-80 part;
Filler 0-50 part;
Sulfhydryl compound, its content is that the ratio of the wherein amount of the amount of thiol compound and the epoxy of epoxy resin is 0.05-0.3:1;
Acid anhydrides, its content is that wherein acid anhydrides amount of substance is 0.7-1.0:1 with the ratio of the amount of the epoxy of epoxy resin.
In the present invention, described epoxy resin is one or more epoxy resin that are selected from Racemic glycidol ethers or glycidyl ester class.
In the present invention, described glycidyl ether based epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin or Resorcinol type epoxy resin.
In the present invention, described glycidyl ester based epoxy resin is selected from tetrahydrophthalic acid 2-glycidyl ester, o-phthalic acid diglycidyl ester, Diglycidyl M-phthalate or hexahydrophthalic acid 2-glycidyl ester.
In the present invention, described toughner is one or more toughner that are selected from rubber elastomer, urethane, polysiloxane, polyacrylic ester or thermoplastic resin.
In the present invention, described filler is the filler of nano level or micro/nano level, and it is one or more fillers that are selected from silicon-dioxide, titanium dioxide, carbon nanotube, zinc oxide, aluminum oxide, calcium carbonate or fiber.
In the present invention, described sulfhydryl compound is one or more sulfhydryl compounds that are selected from polythiol, liquid polysulphide rubber or mercaptan.
In the present invention, described acid anhydrides is the acid anhydrides that liquid state or fusing point are lower, and it is one or more acid anhydrides that are selected from Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, dodecyl Succinic anhydried, 647 acid anhydrides or 70 acid anhydrides.
In the present invention, described epoxy-acid anhydrides tackiness agent is at 25 DEG C of temperature, and 48h is completely curing; At the temperature that is greater than 25 DEG C, completely curing in 48h; The shearing resistance of this epoxy-acid anhydrides tackiness agent is 25-36MPa, and tensile strength is 42-63MPa.
The preparation method of epoxy-acid anhydrides tackiness agent of the present invention comprises the following steps:
A, heating and melting at the temperature by solid-state acid anhydrides more than fusing point, viscosity be more than 40Pa.s epoxy resin and/or toughner be warming up to 40-70 DEG C for subsequent use;
B, adds each raw material to join in glue container, and after stirring, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent.
To explain the present invention below.
A kind of room-temperature curing epoxy-acid anhydrides tackiness agent, it is to contain following component: in weight part
100 parts of epoxy resin;
Toughner 20-80 part;
Filler 0-50 part;
Sulfhydryl compound, its content is that the ratio of the wherein amount of the amount of thiol compound and the epoxy of epoxy resin is 0.05-0.3:1;
Acid anhydrides, its content is that wherein acid anhydrides amount of substance is 0.7-1.0:1 with the ratio of the amount of the epoxy of epoxy resin.
The present invention regulates intensity and the toughness of tackiness agent by toughner and filler, the sulfhydryl compound adding not only can reduce activation energy of curing reaction, and participates in forming crosslinking curing network, does not affect cured article storage, the stability of use procedure.
In the present invention, described epoxy resin is one or more epoxy resin that are selected from Racemic glycidol ethers or glycidyl ester class.
Wherein, glycidyl ether based epoxy resin is by forming containing the phenols of reactive hydrogen or alcohols and epoxy chloropropane polycondensation; Glycidyl ester based epoxy resin is the compound that contains two or more Racemic glycidol ester groups in molecular structure, in the molecule of this based epoxy resin, contain the Racemic glycidol ester bond that polarity is stronger, therefore compare with glycidyl ether based epoxy resin, its reactive behavior is large, bonding strength is high, and available amine, anhydrides and imidazole curing agent solidify.Glycidyl ester based epoxy resin has ambient-temp-stable during by anhydride-cured, and working life is long, and the fast feature of heating after fixing is well suited for as electronics and the embedding of electrical equipment, the insulating material of sealing, casting and flood.
In the present invention, described glycidyl ether based epoxy resin is selected from bisphenol A type epoxy resin (as epoxy resin E-51, E44, E54, E39), bisphenol f type epoxy resin (as CYDF-180) or Resorcinol type epoxy resin (as 680 epoxies, J-80 epoxy).
In the present invention, described glycidyl ester based epoxy resin is selected from tetrahydrophthalic acid 2-glycidyl ester (as 711), o-phthalic acid diglycidyl ester (as 731), Diglycidyl M-phthalate (as 732) or hexahydrophthalic acid 2-glycidyl ester (as CY-183).
In the present invention, described toughner is one or more toughner that are selected from rubber elastomer, urethane, polysiloxane, polyacrylic ester or thermoplastic resin.Preferred rubber elastomerics and/or urethane.
Described rubber elastomer is as hydroxy'terminated butadiene nitrile rubber, nbr carboxyl terminal etc.; Described urethane is as Polyethylene Glycol-600 and 4, the base polyurethane prepolymer for use as of 4 '-diphenylmethane diisocyanate resin (MDI), polytetrahydrofuran diol (PTMG-1000) and 4, the base polyurethane prepolymer for use as of 4 '-'-diphenylmethane diisocyanate (MDI), cetomacrogol 1000 and 4, the base polyurethane prepolymer for use as of 4 '-'-diphenylmethane diisocyanate (MDI) etc.; Described polyacrylic ester is as n-butyl acrylate (BA)/methyl methacrylate (MMA)/glycidyl methacrylate (GMA) copolymer p (MMA-BA-GMA).
Toughner refers to can increase the flexible material of tackiness agent rete.After epoxyn solidifies, elongation is low, and fragility is larger, in the time that bearing external force, bonding position is easy to crack, and expansion rapidly, causing glue-line cracking, not antifatigue, can not serve as the bonding use of structure.Therefore, must manage to reduce fragility, increase toughness, improve loading strength.Toughner generally all contains active group, can with resin generation chemical reaction, not exclusively compatible after solidifying, sometimes also want phase-splitting, can obtain comparatively ideal toughening effect, make heat-drawn wire constant or decline very micro-ly, and shock resistance has clear improvement.
In the present invention, described filler is the filler of nano level or micro/nano level, and it is one or more fillers that are selected from silicon-dioxide, titanium dioxide, carbon nanotube, zinc oxide, aluminum oxide, calcium carbonate or fiber.
In the present invention, described sulfhydryl compound is that one or more are selected from polythiol (as EH-316 polythiol, 3800 polythiols), liquid polysulphide rubber (as 121 thiorubber) or mercaptan.Preferably thiorubber.
Described thiorubber is the low-molecular weight polymer that two ends have thiol group, and it has the excellent properties such as low temperature kindliness, solvent resistance, stress relaxation.The present invention utilizes the high reactivity of sulfydryl in sulfhydryl compound, make at a lower temperature epoxy ring-opening, the hydroxyl of generation can with anhydride reaction, thereby reduced the activation energy of reaction.
Activation energy refers to that molecule changes the needed least energy of active state of easy generation chemical reaction into from normality.Activation energy is less, and the temperature of reacting required is lower.
The present invention adopts dsc (DSC) to characterize activation energy.Differential scanning method is a kind of thermal analysis system.Under programed temperature, measure the difference power of material and reference substance and the relation of temperature of being defeated by.It is with the speed of sample neither endothermic nor exothermic, and rate of heat flow is ordinate zou, taking temperature or time as X-coordinate, can measure multiple thermodynamics and kinetics parameter.Adopt the apparent activation energy of Kissinger equation and the reaction of Ozawa Equation for Calculating by the method.
The present invention adopts Ozawa method, shown in (1).According to Ozawa equation, with In β, to 1/Tp, mapping obtains linear fit straight line, obtains straight slope, can be calculated reaction apparent activation energy.
Wherein β is temperature rise rate (DEG C/min); Tp is peak temperature (K); R is ideal gas constant (molK); E is apparent activation energy.
In the present invention, described acid anhydrides is the acid anhydrides that liquid state or fusing point are lower, and it is one or more acid anhydrides that are selected from Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, dodecyl Succinic anhydried, 647 acid anhydrides or 70 acid anhydrides.
In the present invention, described epoxy-acid anhydrides tackiness agent is at 25 DEG C of temperature, and 48h is completely curing; At the temperature that is greater than 25 DEG C, completely curing in 48h; The shearing resistance of this epoxy-acid anhydrides tackiness agent is 25-36MPa, and tensile strength is 42-63MPa.
The shearing resistance of tackiness agent of the present invention and tensile property are tested respectively with reference to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " and GB/T1447-2005 " fibre reinforced plastics Erichsen test method ".
In the present invention, the preparation method of described epoxy-acid anhydrides tackiness agent comprises the following steps:
A, heating and melting at the temperature by solid-state acid anhydrides more than fusing point, viscosity be more than 40Pa.s epoxy resin and/or toughner be warming up to 40-70 DEG C for subsequent use;
B, adds each raw material to join in glue container, and after stirring, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent.
The object of melting or intensification is in order fully to mix.
The present invention compared with prior art, has following beneficial effect:
(1) epoxy-acid anhydrides adhesive solidification temperature of prior art is high or set time is longer; And epoxy-acid anhydrides tackiness agent of the present invention is in the situation that using curing catalyst, can be at the temperature of 25 DEG C, 48h is completely curing, has expanded the range of application of epoxy-acid anhydrides tackiness agent;
(2) epoxy-acid anhydrides tackiness agent of the present invention is adapted to material that heat resisting temperature is lower or bonding, the embedding of parts, and the unsticking problem that can avoid hot setting heating and cooling to expand with heat and contract with cold causing;
(3) bonding strength of the present invention is greater than 20MPa, can meet conventional bonding, embedding needs.
(4) epoxy-acid anhydrides adhesive raw materials of the present invention is generally easy to get, and preparation method is easy, can reduce production costs;
Brief description of the drawings
Fig. 1 is the Ozawa equation linear fit straight line of embodiment 9 tackiness agent 1;
Fig. 2 is the Ozawa equation linear fit straight line of comparative example's 1 tackiness agent 2.
Embodiment
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Embodiment 1:
647 acid anhydrides are for subsequent use at 50 DEG C～65 DEG C heating and meltings.7 parts of 70 parts of E-51 epoxy resin, 30 parts of 711 epoxy resin, 40 parts of 121 thiorubber (molecular weight 1000), 40 parts of hydroxy'terminated butadiene nitrile rubbers, 70 parts, 647 acid anhydrides, nano silicon are sequentially added into and are joined in glue container, after being uniformly mixed, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent that can use 25 DEG C and above temperature-curable.
At 25 DEG C of curing 48h, the shearing resistance that records bonding Ly12 under room temperature according to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " is 30.7MPa, and the tensile strength that records tackiness agent with reference to GB/T1447-2005 " fibre reinforced plastics Erichsen test method " is 49.3MPa.
Embodiment 2
647 acid anhydrides are for subsequent use at 50 DEG C～65 DEG C heating and meltings.By 80 parts of E-51 epoxy resin, 20 parts of 680 epoxy resin, 41 parts of liquid polysulfide rubbers (molecular weight 3000), Polyethylene Glycol-600 and 4,40 parts of 20 parts of the base polyurethane prepolymer for use as (molecular weight 6000) of 4 '-'-diphenylmethane diisocyanate (MDI), 20 parts, 647 acid anhydrides, 70 acid anhydrides are sequentially added into joins in glue container, after being uniformly mixed, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent that can use 25 DEG C and above temperature-curable.
At 25 DEG C of curing 48h, the shearing resistance that records bonding Ly12 under room temperature according to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " is 35.8MPa, and the tensile strength that records tackiness agent with reference to GB/T1447-2005 " fibre reinforced plastics Erichsen test method " is 58.7MPa.
Embodiment 3
Tetra Hydro Phthalic Anhydride is for subsequent use at 70 DEG C～90 DEG C heating and meltings, E-44 epoxy resin is added to hot reserve at 50 DEG C～65 DEG C.By 40 parts of E-44 epoxy resin, 60 parts of 711 epoxy resin, 81 parts of liquid polysulfide rubbers (molecular weight 1000), Polyethylene Glycol-600 and 4,5 parts of 30 parts of the base polyurethane prepolymer for use as (molecular weight 6000) of 4 '-'-diphenylmethane diisocyanate (MDI), 20 parts of Tetra Hydro Phthalic Anhydrides, 15 parts, 70 acid anhydrides, 10 parts of nano titanium oxides, carbon nanotube are sequentially added into joins in glue container, after being uniformly mixed, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent that can use 25 DEG C and above temperature-curable.
At 35 DEG C of curing 20h, the shearing resistance that records bonding Ly12 under room temperature according to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " is 25.7MPa, and the tensile strength that records tackiness agent with reference to GB/T1447-2005 " fibre reinforced plastics Erichsen test method " is 61.5MPa.
Embodiment 4
Hexahydrophthalic anhydride is for subsequent use at 50 DEG C～60 DEG C heating and meltings.By 70 parts of CYDF-180 bisphenol F epoxy resins, 30 parts of 680 epoxy resin, 10 parts of EH-316 polythiols, polytetrahydrofuran diol (PTMG-1000) and 4,20 parts of 10 parts of the base polyurethane prepolymer for use as (molecular weight 8000) of 4 '-'-diphenylmethane diisocyanate (MDI), 15 parts of hydroxy'terminated butadiene nitrile rubbers, 50 parts of hexahydrophthalic anhydrides, nano aluminium oxide are sequentially added into joins in glue container, after being uniformly mixed, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent that can use 25 DEG C and above temperature-curable.
At 25 DEG C of curing 48h, the shearing resistance that records bonding Ly12 under room temperature according to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " is 27.4MPa, and the tensile strength that records tackiness agent with reference to GB/T1447-2005 " fibre reinforced plastics Erichsen test method " is 46.5MPa.
Embodiment 5
E-44 epoxy resin is added to hot reserve at 50 DEG C～65 DEG C.20 parts of 50 parts of E-44 epoxy resin, 30 parts of 680 epoxy resin, 20 parts of 711 epoxy resin, 10 parts of 3800 polythiols, 20 parts of n-butyl acrylate (BA)/methyl methacrylate (MMA)/glycidyl methacrylate (GMA) copolymer ps (MMA-BA-GMA), 31 parts, 70 acid anhydrides, nano zine oxide are sequentially added into and are joined in glue container, after being uniformly mixed, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent that can use 25 DEG C and above temperature-curable.
At 30 DEG C of curing 30h, the shearing resistance that records bonding Ly12 under room temperature according to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " is 23.7MPa, and the tensile strength that records tackiness agent with reference to GB/T1447-2005 " fibre reinforced plastics Erichsen test method " is 53.5MPa.
Embodiment 6
647 acid anhydrides are for subsequent use at 50 DEG C～65 DEG C heating and meltings.2 parts of 70 parts of CYDF-180 bisphenol F epoxy resins, 30 parts of 711 epoxy resin, 50 parts of liquid polysulfide rubbers (molecular weight 3000), 10 parts of EH-316 polythiols, 80 parts of nbr carboxyl terminals, 20 parts, 647 acid anhydrides, 20 parts, 70 acid anhydrides, 5 parts of nano aluminium oxides, nano silicon are sequentially added into and are joined in glue container, after being uniformly mixed, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent that can use 25 DEG C and above temperature-curable.
At 25 DEG C of curing 48h, the shearing resistance that records bonding Ly12 under room temperature according to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " is 31.7MPa, and the tensile strength that records tackiness agent with reference to GB/T1447-2005 " fibre reinforced plastics Erichsen test method " is 42.8MPa.
Embodiment 7
Tetra Hydro Phthalic Anhydride is for subsequent use at 70 DEG C～90 DEG C heating and meltings, E-44 epoxy resin is added to hot reserve at 50 DEG C～65 DEG C.By 50 parts of E-51 epoxy resin, 50 parts of E-44 epoxy resin, 10 parts of liquid polysulfide rubbers (molecular weight 1000), 5 parts of EH-316 polythiols, cetomacrogol 1000 and 4,5 parts of 45 parts of the base polyurethane prepolymer for use as (molecular weight 8000) of 4 '-'-diphenylmethane diisocyanate (MDI), 18 parts of hexahydrophthalic anhydrides, 20 parts, 70 acid anhydrides, 5 parts of nano aluminium oxides, carbon nanotube are sequentially added into joins in glue container, after being uniformly mixed, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent that can use 25 DEG C and above temperature-curable.
At 25 DEG C of curing 48h, the shearing resistance that records bonding Ly12 under room temperature according to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " is 32.6MPa, and the tensile strength that records tackiness agent with reference to GB/T1447-2005 " fibre reinforced plastics Erichsen test method " is 53.4MPa.
Embodiment 8
647 acid anhydrides, E-44 epoxy resin are added to hot reserve at 50 DEG C～65 DEG C.5 parts of 60 parts of E-44 epoxy resin, 40 parts of 680 epoxy resin, 5 parts of 121 thiorubber (molecular weight 1000), 10 parts of 3800 polythiols, 60 parts of hydroxy'terminated butadiene nitrile rubbers, 50 parts, 647 acid anhydrides, 10 parts, 70 acid anhydrides, 5 parts of nano silicons, nano aluminium oxide are sequentially added into and are joined in glue container, after being uniformly mixed, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent that can use 25 DEG C and above temperature-curable.
At 25 DEG C of curing 48h, the shearing resistance that records bonding Ly12 under room temperature according to GB/T7124-2008 " mensuration of tackiness agent tensile shear strength " is 27.5MPa, and the tensile strength that records tackiness agent with reference to GB/T1447-2005 " fibre reinforced plastics Erichsen test method " is 53.7MPa.
Embodiment 9
7 parts of 70 parts of E-51 epoxy resin, 30 parts of 711 epoxy resin, 40 parts of 121 thiorubber (molecular weight 1000), 40 parts of hydroxy'terminated butadiene nitrile rubbers, 70 parts, 647 acid anhydrides, nano silicon are mixed with to tackiness agent 1, adopt dsc (DSC) to characterize, probe temperature is 20-600 DEG C, temperature rise rate is respectively 5 DEG C/min, 10 DEG C/min, 15 DEG C/min and 200 DEG C/min, nitrogen atmosphere.
According to Ozawa equation (seeing formula 1), with In β, to 1/Tp, mapping obtains linear fit straight line, sees Fig. 1.
Fig. 1 straight slope is-0.258, and in substitution formula (1), the apparent activation energy that calculates this tackiness agent is 20.11kJ/mol.
Comparative example 1
7 parts of 70 parts of E-51 epoxy resin, 30 parts of 711 epoxy resin, 40 parts of hydroxy'terminated butadiene nitrile rubbers, 70 parts, 647 acid anhydrides, nano silicon are mixed with to tackiness agent 2, adopt dsc (DSC) to characterize, probe temperature is 20-600 DEG C, temperature rise rate is respectively 5 DEG C/min, 10 DEG C/min, 15 DEG C/min and 200 DEG C/min, nitrogen atmosphere.
According to Ozawa equation (seeing formula 1), with In β, to 1/Tp, mapping obtains linear fit straight line, sees Fig. 2.
Fig. 2 straight slope is-7.916, and in substitution formula (1), the apparent activation energy that calculates this tackiness agent is 617.03kJ/mol.
This embodiment is the comparative example of embodiment 9; Add the apparent activation energy of 121 thiorubber front and back tackiness agent visible by contrasting two embodiment, add after 121 thiorubber, apparent activation energy reduces greatly, and therefore, the temperature that adds the epoxy-acid anhydrides adhesive solidification after 121 thiorubber to react required is lower.This experimental data shows, the formula system of epoxy-acid anhydrides tackiness agent of the present invention can reduce the solidification value of prior art epoxy-acid anhydrides tackiness agent.
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only preferably embodiment of the present invention, embodiments of the present invention are not restricted to the described embodiments, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiments, within these amendments and embodiment will drop on the disclosed principle scope and spirit of the application.
Claims (10)
1. room-temperature curing epoxy-acid anhydrides tackiness agent, is characterized in that this epoxy-acid anhydrides tackiness agent contains following component: in weight part
100 parts of epoxy resin;
Toughner 20-80 part;
Filler 0-50 part;
Sulfhydryl compound, its content is that the ratio of the wherein amount of the amount of thiol compound and the epoxy of epoxy resin is 0.05-0.3:1;
Acid anhydrides, its content is that wherein acid anhydrides amount of substance is 0.7-1.0:1 with the ratio of the amount of epoxy resin epoxy.
2. epoxy-acid anhydrides tackiness agent according to claim 1, is characterized in that described epoxy resin is one or more epoxy resin that are selected from Racemic glycidol ethers or glycidyl ester class.
3. epoxy-acid anhydrides tackiness agent according to claim 2, is characterized in that described Racemic glycidol ethers epoxy tree is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin or Resorcinol type epoxy resin.
4. epoxy-acid anhydrides tackiness agent according to claim 2, is characterized in that described glycidyl ester based epoxy resin is selected from tetrahydrophthalic acid 2-glycidyl ester, o-phthalic acid diglycidyl ester, Diglycidyl M-phthalate or hexahydrophthalic acid 2-glycidyl ester.
5. epoxy-acid anhydrides tackiness agent according to claim 1, is characterized in that described toughner is one or more toughner that are selected from rubber elastomer, urethane, polysiloxane, polyacrylic ester or thermoplastic resin.
6. epoxy-acid anhydrides tackiness agent according to claim 1, it is characterized in that described filler is the filler of nano level or micro/nano level, it is one or more fillers that are selected from silicon-dioxide, titanium dioxide, carbon nanotube, zinc oxide, aluminum oxide, calcium carbonate or fiber.
7. epoxy-acid anhydrides tackiness agent according to claim 1, is characterized in that described sulfhydryl compound is one or more sulfhydryl compounds that are selected from polythiol, liquid polysulphide rubber or mercaptan.
8. epoxy-acid anhydrides tackiness agent according to claim 1, it is characterized in that described acid anhydrides is the acid anhydrides that liquid state or fusing point are lower, it is one or more acid anhydrides that are selected from Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, dodecyl Succinic anhydried, 647 acid anhydrides or 70 acid anhydrides.
9. according to the epoxy-acid anhydrides tackiness agent described in claim 1-8 any one, it is characterized in that described epoxy-acid anhydrides tackiness agent is at 25 DEG C of temperature, 48h is completely curing; At the temperature that is greater than 25 DEG C, completely curing in 48h; The shearing resistance of this epoxy-acid anhydrides tackiness agent is 25-36MPa, and tensile strength is 42-63MPa.
10. according to the preparation method of the epoxy-acid anhydrides tackiness agent described in claim 1-8 any one, it is characterized in that this preparation method comprises the following steps:
A, by solid-state acid anhydrides heating and melting at the above temperature of fusing point, viscosity be more than 40Pa.s epoxy resin and/or toughner be warming up to 40-70 DEG C for subsequent use;
B, adds each raw material to join in glue container, and after stirring, vacuum defoamation, obtains epoxy-acid anhydrides tackiness agent.
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