CN102911631A - Adhesive composition with single-component epoxy structure - Google Patents
Adhesive composition with single-component epoxy structure Download PDFInfo
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- CN102911631A CN102911631A CN 201110223383 CN201110223383A CN102911631A CN 102911631 A CN102911631 A CN 102911631A CN 201110223383 CN201110223383 CN 201110223383 CN 201110223383 A CN201110223383 A CN 201110223383A CN 102911631 A CN102911631 A CN 102911631A
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Abstract
The invention relates to an adhesive composition with a single-component epoxy structure. The adhesive composition comprises at least one unmodified epoxy resin, a toughness modified epoxy resin, a polyether amine modified epoxy prepolymer, a damp and heat ageing resistant additive comprising a carbodiimide structure, a curing agent, an optional curing accelerator, an optional phosphating modified epoxy resin, and one or more of other optional components as follows: a filling, a monofunctional epoxy reaction type diluent, a thixotropic agent and a mixture thereof.
Description
Technical field
The present invention relates to a kind of binder composition, more specifically relate to a kind of single-component epoxy structure binder composition.
Background technology
Tackiness agent is widely used in the fields such as packing, building, automobile, electronics, shoemaking, weaving, plastics, timber, optics, health care, space flight and aviation, sea transport as a family macromolecule material.But along with the raising to the performance requriements of material, the ageing failure problem of tackiness agent is day by day serious, reaches far away the level that adapts with the material practical application, has greatly limited exploitation and the application of tackiness agent novel material.
Epoxy resin binder has good adhesiveproperties to materials such as metal, plastics, glass, potteries, after bonding curing, have good mechanical property, electrical insulation properties, thermotolerance and chemical resistance, thereby all be widely used at aspects such as mechanical workout manufacturing, electric, aerospace, shipbuilding, automobile, construction.As the transmitted load body material, because epoxy resin structural itself contains a lot of hydroxyls, these hydroxyls are subject to the impact of external environment (for example light, oxygen, water, heat), reduce the mechanical property of material, thus the mechanical property that further endangers matrix material.The researchist is at the initial stage of bonded structure development both at home and abroad, and what mainly value is the bonded structure performance, has often ignored the endurance issues of tackiness agent self.
Document (Wang Wenjun etc., bonding, 2006,27 (1): the epoxy building adhesive of introducing 10～11) was through 500 hours hydrothermal aging (50 ℃ of wet heat conditions, 95% humidity) strength degradation after reaches more than 60%, document (Zhang Hui etc., the Arms Material scientific and engineering, 2010,33 (3): the epoxy resin-based adhesive of introducing 41～43) is at 80 ℃, through behind 500 hours aging, shearing resistance descends and reaches about 40% under the hydrothermal aging condition of 90% humidity.
For this reason, the research of tackiness agent environmental behaviour and failure mechanism has been subject to the attention of height.For example, Chinese patent CN1978526 and CN101085855 all report a kind of silicone resin modified epoxy matrix that adopts and obtain a kind of epoxy adhesive with uvioresistant, heat resistant performance.Because use silicone resin and Resins, epoxy reaction, so that manufacturing cost is higher, technique is complexity, intensity relatively a little less than.
For this reason, develop that a kind of wet and heat ageing resistant excellent performance, preparation method are simple, starting material are easy to get, the epoxy construction tackiness agent of adhesive property excellence is to the application of developing epoxy structural rubber and prolong the work-ing life of glueing joint product and be badly in need of very much.
Summary of the invention
The present invention relates to a kind of wet and heat ageing resistant excellent property, single-component epoxy structure glue adhesive composition that cohesive strength is high.
The invention provides a kind of single-component epoxy structure binder composition, it comprises:
-at least a unmodified epoxy resin;
-toughness modified epoxy;
-polyethex amine modification epoxy prepolymer;
-contain the wet and heat ageing resistant additive of carbodiimide structure;
-solidifying agent;
-optional the curing catalyst that exists;
-optional phosphatization the modified epoxy that exists; And
One or more of-optional existence are selected from other following components: filler, monofunctional epoxy response type thinner, thixotropic agent and their mixture.
In one embodiment of the invention, described single-component epoxy structure binder composition comprises: at least a unmodified epoxy resin of 100 weight parts; 250～400 weight parts or 270-380 weight part toughness modified epoxy; 90-160 weight part or 100～150 weight part polyethex amine modification epoxy prepolymers; 0.5-10 weight part or 0.8-7 weight part contain the wet and heat ageing resistant additive of carbodiimide structure; 20-70 weight part or 25～60 weight part Dyhard RU 100 class solidifying agent; 1.5-3.5 the optional ureas curing catalyst that exists of weight part or 2-3 weight part; The optional phosphatization modified epoxy that exists of 80-170 weight part or 100～150 weight parts; The optional filler that exists of 80～220 weight parts or 90-200 weight part; The optional monofunctional epoxy response type thinner that exists of 10～50 weight parts or 12-40 weight part; And the optional thixotropic agent that exists of 25～55 weight part or 30～50 weight parts.
The wet and heat ageing resistant excellent property of epoxy adhesive of the present invention, aging after high, the T-shaped stripping strength of shearing resistance of tackiness agent high, the high energy surface of metal, pottery, glass and polymkeric substance is all had good cohesiveness.
It is pointed out that in the present invention, when having provided concrete upper and lower ends point value for arbitrary numerical range, its scope comprises the arbitrary value within the described endpoint value and equals or about the value that equals arbitrary endpoint value.
Embodiment
Unless otherwise indicated, all publications that the present invention mentions, patent application, patent and other reference all are incorporated into herein by reference in full, are equivalent to be presented in full this paper.
Unless otherwise defined, all technology used herein and scientific terminology have the common same implication of understanding of one skilled in the art of the present invention.In the situation that conflict, comprise that with this specification sheets definition is as the criterion.
Unless otherwise indicated, all percentage ratio, umber, ratio etc. are all by weight.
Term used herein " by ... make " and " comprising " synonym.Term used herein " comprises ", " comprising ", " containing ", " having " or its any other variant, is intended to contain nonexcludability and comprises.For example, the composition, technique, method, goods or the device that comprise a series of key elements not necessarily only limit to those key elements, but can comprise other key element of clearly not enumerating, perhaps other intrinsic key element of composition, technique, method, goods or device so.
When explaining certain amount, concentration or other value or parameter with the form of scope, preferable range or preferred numerical upper limits and preferred numerical lower limits, be to be understood that to be equivalent to specifically to have disclosed any scope that combines by with any a pair of range limit or preferred value and any range lower limit or preferred value, and should do not consider whether this scope specifically discloses.Unless otherwise noted, the listed numerical range of this paper is intended to comprise the end points of scope, and all integers and mark within this scope.
The present invention relates to a kind of single component wet and heat ageing resistant epoxy structural adhesive composition, it comprises:
-at least a unmodified epoxy resin;
-toughness modified epoxy;
-polyethex amine modification epoxy prepolymer;
-contain the wet and heat ageing resistant additive of carbodiimide structure;
-solidifying agent;
-optional the curing catalyst that exists;
-optional phosphatization the modified epoxy that exists; And
One or more of-optional existence are selected from other following components: filler, monofunctional epoxy response type thinner, thixotropic agent and their mixture.
Term used herein " construction adhesive " has this area implication commonly used, refer to that specifically intensity is high, can bear larger load and ageing-resistant, antifatigue, corrosion-resistant, stable performance in predicted life is applicable to bear the powerful bonding tackiness agent of structural part.
Term used herein " epoxy construction tackiness agent " also is called " epoxy resin structural tackiness agent ", refers to the construction adhesive of Resins, epoxy as main ingredient.
Term used herein " unmodified epoxy resin " refers to not pass through the Resins, epoxy of modification, and the Resins, epoxy that namely is purchased directly uses without any processing.Its refer to per molecule have at least one 1, the polyepoxide of 2-epoxy group(ing), this polyepoxide can be the polyepoxides of saturated, undersaturated, ring-type or acyclic, aliphatic, alicyclic, aromatics or heterocycle.Preferably, be used for the Resins, epoxy of the present composition, on average comprise at least two 1 in its per molecule, the 2-epoxy group(ing).
In embodiments of the invention, unmodified epoxy resin particularly preferably uses liquid epoxies, and at room temperature the epoxy equivalent (weight) of liquid epoxies normally approximately 150 to approximately 480, particularly preferably bisphenol A-type or bisphenol f type epoxy resin.
In the present invention, unmodified epoxy resin can use separately, also can two or more mix use.In a preferred embodiment, used bisphenol A type epoxy resin.The example of bisphenol A type epoxy resin is the commercially available prod such as E51, E44, EPON828 and EPON826.
Term used herein " toughness modified epoxy " refers to the product that can effectively strengthen room-temperature curing epoxy structural tackiness agent toughness that Resins, epoxy is obtained after treatment.In a preferred embodiment of the invention, the preferred toughness modified epoxy that uses for liquid nitrile rubber (CTBN) modification and/or with the toughness reinforcing Resins, epoxy of polymkeric substance (core shell latex polymer) of nucleocapsid structure, more preferably use the bisphenol A type epoxy resin of liquid nitrile rubber modification and/or with the bisphenol A type epoxy resin of the polymer toughening of nucleocapsid structure.
The bisphenol A type epoxy resin of described liquid nitrile rubber modification can obtain by buying on the market, also can obtain with reference to this area ordinary method.In a preferred embodiment of the invention, the bisphenol A type epoxy resin of CTBN modification is made by following preparation method: under 20～30 ℃ 100 weight part liquid nitrile rubbers, 240～260 weight part bisphenol A type epoxy resins, 2～3 weight part aerosils are mixed with 2～3 weight part phenyltrimethoxysila,e, be heated to 60～70 ℃, reacted 3～4 hours, after the cooling and get final product.Wherein, bisphenol A type epoxy resin described here is preferably E51, E44, EPON828 or EPON826; The speed of heating is preferably 2～5 ℃/minutes, preferably is cooled to 20～25 ℃.
The Resins, epoxy of described polymer toughening with nucleocapsid structure refers to and will have the polymkeric substance of nucleocapsid structure and the product that epoxy blend obtains.Here used Resins, epoxy particularly preferably uses liquid epoxies, namely at room temperature is the Resins, epoxy of liquid, its epoxy equivalent (weight) normally approximately 150 to approximately 480, the particularly preferably Resins, epoxy of liquid bisphenol A-type or Bisphenol F type.Resins, epoxy can use separately, also can two or more mix use.In a preferred embodiment, used liquid bisphenol A epoxy resin.The example of bisphenol A type epoxy resin is the commercially available prod such as E51, E44, EPON828 and EPON826.
The polymkeric substance of nucleocapsid structure has nuclear, this nuclear comprises and has elastomerics shape or rubber-like characteristic the polymeric material of (be second-order transition temperature less than approximately 0 ℃, for example less than approximately-30 ℃), described nuclear is surrounded by shell, it (is thermoplasticity or thermoset/crosslinked polymkeric substance that this shell comprises the non-elastomer polymer material, the second-order transition temperature of this polymkeric substance is greater than envrionment temperature, for example greater than approximately 50 ℃).For example, this endorses to comprise diene homopolymer or the multipolymer (homopolymer of divinyl or isoprene for example, divinyl or isoprene and one or more are such as vi-ny l aromatic monomers, (methyl) vinyl cyanide, and this shell can comprise one or more such as (methyl) acrylate (for example methyl methacrylate) multipolymer of the ethylenically unsaturated monomers of (methyl) acrylate and so on),, vi-ny l aromatic monomers (for example vinylbenzene), vinyl cyanide (for example vinyl cyanide), unsaturated acid and acid anhydrides (for example vinylformic acid), polymkeric substance with suitable high glass-transition temperature or the multipolymer of (methyl) acrylamide etc. and so on monomer.The polymkeric substance or the multipolymer that are used for this shell can have acidic group, and this acidic group is ion ground crosslinked (for example by forming the salt of divalent metal) by forming metal carboxylate.This shell polymeric or multipolymer also may be covalently crosslinked by using per molecule to have a monomer of two or more pairs of keys.The outside surface of this shell can be used the group functionalization such as the carboxylic acid group.Other rubber elastomer that comprises butyl polyacrylate or silicone elastomer (for example polydimethylsiloxane, particularly crosslinked polydimethylsiloxane) also is applicable to nuclear.
Polymkeric substance with nucleocapsid structure can prepare according to the ordinary skill in the art, also can obtain from several commercial source, for example: can be from Wacker Chemie by the nucleocapsid particles of trade name GENIOPERL with the powder type acquisition, comprise GENIOPERL P22, P23, P52 and P53, can be from Rohm﹠amp; Core shell rubber particles, particularly PARALOID EXL 2600/3600 series product that Haas obtains by trade name PARALOID, by Roehm GmbH or Roehm America, the core shell rubber particles of Inc. selling by trade name DEGALAN (DEGALAN 4899F for example, its second-order transition temperature is approximately 95 ℃ according to reports), by the core shell rubber particles of Nippon zeon by trade name F351 sale, and by the core shell rubber particles of General Electric by trade name BLENDEX sale.
To be that this area is conventional use the bisphenol A type epoxy resin of the polymer toughening of used nucleocapsid structure among the present invention, can buy to obtain, and for example is preferably among MX125, MX153, MX157 and the MX257 of KANEKA company production one or more.Except direct purchase, the Resins, epoxy of described polymer toughening with nucleocapsid structure also can be prepared with reference to this area ordinary method.
In the embodiment of the polymkeric substance of nucleocapsid structure of the present invention, examine the rubber elastomer into this area routine, shell is polystyrene.
Bisphenol A type epoxy resin toughening mechanism with the polymer toughening of nucleocapsid structure mainly is to utilize " void effect "; between nuclear and shell, a layer space arranged; when extraneous power arrived core-shell particles by resin, this layer space can sorption power, thereby play the effect of protective colloid; referring to document: Qiu Hongbin; Dong Lisong, Feng Zhiliu, polymer circular; 1997,3:179～183.
Term used herein " polyethex amine modification epoxy prepolymer " refers to the product that Resins, epoxy and polyetheramine react, and wherein, the epoxide group in the Resins, epoxy does not have complete reaction, has still kept a part of epoxy group(ing).
The Resins, epoxy that uses in the used polyethex amine modification epoxy prepolymer of preparation the present invention particularly preferably is liquid epoxies, namely at room temperature be the Resins, epoxy of liquid, its epoxy equivalent (weight) normally approximately 150 to approximately 250, the particularly preferably Resins, epoxy of bisphenol A-type or Bisphenol F type.Epoxy compounds can use separately, also can two or more mix use.In a preferred embodiment, used bisphenol A type epoxy resin.The example of bisphenol A type epoxy resin is the commercially available prod such as E51, E44, EPON828 and EPON826.
In embodiments of the invention, employed polyetheramine is preferably the polyetheramine of number-average molecular weight 200～400 and/or the polyetheramine of number-average molecular weight 2000～5000, wherein the weight ratio of the polyetheramine of the polyetheramine of molecular weight 200～400 and molecular weight 2000～5000 is 1: 1.3～1: 1.1, is preferably 1: 1～1: 1.1.Described number-average molecular weight is 200～400 polyetheramine, is preferably polyetheramine T403 and/or polyetheramine D230; Described number-average molecular weight is 2000～5000 polyetheramine, is preferably polyetheramine T5000 and/or polyetheramine D2000.
The prepolymer of described polyetheramine and bisphenol A epoxide resin can adopt this area ordinary method preparation.In a preferred embodiment, the preparation method is as follows: under 20～30 ℃ 100 weight part bisphenol A epoxide resins, 40～80 weight part polyetheramines, 2～3 weight part phenyltrimethoxysila,e coupling agents are mixed, be heated to 80～100 ℃, reacted 2～2.5 hours, then continue to heat to 120～130 ℃, reacted 1～2 hour, be cooled to 20～25 ℃ after and get final product.Apply mechanical stirring in the whole preparation process, stir speed (S.S.) is at 1000～2000 rev/mins, and the speed of heating is 2～5 ℃/minutes, and the epoxy equivalent (weight) of reacted prepolymer is between 400～600.
The wet and heat ageing resistant agent of using among the present invention contains carbodiimide (N=C=N-) structure, wherein-the N=C=N-structure has strong water sorption, absorb moisture and be transformed into later on urea groups (NH-CO-NH-) the further cured epoxy resin of energy, increase the degree of crosslinking of resin system, improve thermotolerance.
In embodiments of the invention, the wet and heat ageing resistant agent of preferably using is one or more in 300～2000 the polycarbodiimide as dicyclohexyl carbodiimide, phenylbenzene carbodiimide, divinyl carbodiimide, diethyl carbodiimide and number-average molecular weight.Described number-average molecular weight is that the example of 300～2000 polycarbodiimide is the STABAXOL@P, the STABAXOL@100P that produce of Rhein Chemie company, among the STABAXOL@200P one or more.
Because composition of the present invention is single-component composition, it will solidify under heating up, so they also comprise one or more solidifying agent (stiffening agent), this solidifying agent can be realized the crosslinked of some binder ingredients or solidify when the optimal temperature that is heated to when this tackiness agent above room temperature.That is to say, this solidifying agent activates by heating.In the present invention, preferred activation temperature is 150-200 ℃ solidifying agent, and more preferably activation temperature is 160-180 ℃ solidifying agent.
The heat-activatable solidifying agent that goes for tackiness agent of the present invention for example is guanidine, replacement guanidine, replacement urea, melamine resin, guanamines derivative, cyclic tertiary amine, aromatic amine and/or its mixture.The example that replaces guanidine is methylguanidine, dimethylguanidine, trimethylammonium guanidine, tetramethyl guanidine, different two guanidines of methyl, different two guanidines of dimethyl, different two guanidines of tetramethyl-, different two guanidines of hexamethyl, different two guanidines of seven methyl and dicyanodiamide (Dyhard RU 100) class solidifying agent.With regard to single component thermosetting adhesive of the present invention, Dyhard RU 100 class solidifying agent is particularly preferred, especially is preferably Dicyanodiamide (C
2H
4N
4), melamine (C
3H
6N
6), guaranteed thus the storage stability that said composition is good.
In embodiments of the invention, the example of preferred Dyhard RU 100 class solidifying agent is Dyhard 100SH, the Dyhard 100S of Degussa company production, the CG1200 that Air product company produces, one or more among the CG1400.
Described ureas curing catalyst is adhesive field curing catalyst commonly used, is preferably urea (CO (NH
2)
2) or thiourea (SC (NH
2)
2).In embodiments of the invention, be preferably Dyhard UR200, Dyhard UR300, Dyhard UR500, Dyhard UR700, U-52M, the U-405M of CVC company production and one or more among the DDA5 that Degussa company produces.
In single component wet and heat ageing resistant epoxy structural adhesive composition of the present invention, also preferably comprise the phosphatization modified epoxy,
Used " phosphatization modified epoxy " among the present invention also is called phosphatization Resins, epoxy, and its each molecule contains 3 or 3 above epoxide groups.Described phosphatization modified epoxy is preferably the EP49-10N that ADEKA company produces, one or more among the EP49-12N.
At single component wet and heat ageing resistant epoxy structural adhesive composition of the present invention, it also can comprise one or more following components: epoxy reaction type thinner, filler, thixotropic agent or their mixture.
Contain epoxide group in the molecular chain of described epoxy reaction type thinner, can react with the interlinkage that carries out of various solidifying agent, form reticulated structure.Epoxy reaction type thinner is to cooperate basic Resins, epoxy to mix to use, and can reduce curing system viscosity, increases flowability, increases the service life, and is convenient to large-area construction; When having improved operability, do not affect again the fundamental property of cured article.The convenient application that is used for casting, perfusion, bonding, sealing, impregnating aspect.Used epoxy reaction type thinner is preferably simple function among the present invention, namely only has an epoxide group in its each molecule, and its viscosity at 25 ℃ is generally 100～300mPa.s.In embodiments of the invention, preferably use the NC513 of Cardolite company production and one or more among the Lite2513HP.
Described filler is for being used for the customary filler of adhesive field, for example various grindings or the precipitation chalk, silica powder, aluminum oxide, aschistic clay, rhombspar, carbon fiber, glass fibre, polymer-type fiber, titanium dioxide, the silicon-dioxide of calcining, carbon black, calcium oxide, miemite, calcium sulfate, barite and the particularly filler of the similar silicate of magnesium aluminum silicate calcium type, for example wollastonite and chlorite.Described filler is preferably filler fibrous, the micron dimension size, more preferably fibrous wollastonite and/or fibrous calcium sulfate.
Term " thixotropic agent " refers to add in the resin, can make resin adhesive liquid that higher denseness is arranged when static, becomes again under external force the material of low denseness fluid.Can use the thixotropic agent of this area routine in the binder composition of the present invention, for example, aerosil, organobentonite, hydrogenated castor oil, polyamide wax etc.In embodiments of the invention, preferably use aerosil.
Binder composition of the present invention can also comprise other common auxiliary agent and additive, for example softening agent, flow promotor, coupling agent (for example silane), tackifier, wetting agent, tackifier, fire retardant, thixotroping and/or rheology control agent, protective agent and/or inhibiter, stablizer and/or tinting pigment.Depend on processing characteristics, snappiness, desired fixed action and the tackiness agent of tackiness agent to the gluing required requirement of base material, the relative proportion of each component can change in wider limit.
In the present invention, the single-component epoxy structure binder composition comprises: at least a unmodified epoxy resin of 100 weight parts; 250～400 weight parts or 270-380 weight part toughness modified epoxy; 90-160 weight part or 100～150 weight part polyethex amine modification epoxy prepolymers; 0.5-10 weight part or 0.8-7 weight part contain the wet and heat ageing resistant additive of carbodiimide structure; 20-70 weight part or 25～60 weight part Dyhard RU 100 class solidifying agent; 1.5-3.5 the optional ureas curing catalyst that exists of weight part or 2-3 weight part; The optional phosphatization modified epoxy that exists of 80-170 weight part or 100～150 weight parts; The optional filler that exists of 80～220 weight parts or 90-200 weight part; The optional monofunctional epoxy response type thinner that exists of 10～50 weight parts or 12-40 weight part; And the optional thixotropic agent that exists of 25～55 weight part or 30～50 weight parts.
The ageing-resistant epoxy structural rubber of single component of the present invention can be by the preparation of following process: at 40～50 ℃ with at least a unmodified epoxy resin, the toughness modified epoxy, the polyethex amine modification epoxy prepolymer, the optional phosphatization modified epoxy that exists mixes, stir speed (S.S.) is 500～1000 rev/mins, the time of mixing is 10～12 minutes, then in said mixture, add the wet and heat ageing resistant agent, the optional monofunctional epoxy thinner that exists, the optional filler that exists, the optional thixotropic agent that exists, mix, stir speed (S.S.) is 500～1000 rev/mins, and the time of mixing is 10～15 minutes.Then mixture is cooled to 20～30 ℃, adds Dyhard RU 100 class solidifying agent and the optional ureas curing catalyst that exists, mix, stir speed (S.S.) is 500～1000 rev/mins, and the time of mixing is to get final product in 10～15 minutes.
Single component wet and heat ageing resistant epoxy construction adhesive outward appearance of the present invention is jelly, and is nontoxic, tasteless, do not contain any volatile solvent, can be-90 ℃～120 ℃ uses, and its viscosity is between 5000～8000mPa.s under the room temperature.Among the present invention, described room temperature refers to 20～30 ℃.
The solidification value of single component wet and heat ageing resistant epoxy construction adhesive of the present invention is 160～180 ℃, and be 30～40min set time.
Single component wet and heat ageing resistant epoxy construction adhesive of the present invention reaches 32MPa in steel-steel surface shear intensity after solidifying, the T-shaped stripping strength on steel-steel surface reaches 11N/mm, glue is through after being immersed in the water 500h under 70 ℃, reach 28MPa in steel-steel surface shear intensity, the T-shaped stripping strength on steel-steel substrate surface reaches 10N/mm.Aging strength degradation after 1000 hours only is no more than 30%.The lower shelf lives of room temperature was greater than 1 year.High energy surface to metal, pottery, glass and polymkeric substance all has good cohesiveness.
The present invention has the wet and heat ageing resistant agent of special construction by introducing, can greatly improve the wet and heat ageing resistant performance of epoxy resin glue.Introduce simultaneously the Resins, epoxy of toughness modification, so that epoxy structural rubber has low-temperature impact resistance.
Epoxy adhesive of the present invention is nontoxic, tasteless, do not contain any volatile solvent, and the preparation method is simple, and starting material are easy to get, and preparation condition is not harsh.Wet and heat ageing resistant excellent property after it solidifies, high, the T-shaped stripping strength of shearing resistance of aging rear tackiness agent is high.High energy surface to metal, pottery, glass and polymkeric substance all has good cohesiveness.
Because adopt novel wet and heat ageing resistant agent, its principal feature is that water regain is large, can participate in simultaneously the curing reaction of Resins, epoxy with the reacted product of water, strengthen the curing cross-linked degree of system, thereby improve the thermotolerance of tackiness agent.
And owing to adopting CTBN modified bisphenol A type Resins, epoxy or the bisphenol A type epoxy resin with nucleocapsid structure polymer modification, solved the large shortcoming of fragility behind the epoxy resin cure, given epoxy resin binder very high toughness.
Embodiment
The below further specifies the present invention with embodiment, but the present invention is not limited.
Material therefor and source among the embodiment:
E44 Resins, epoxy: bisphenol A type epoxy resin, available from Wuxi resin processing plant;
E51 Resins, epoxy: bisphenol A type epoxy resin, available from Wuxi resin processing plant;
EPON828 Resins, epoxy: bisphenol A type epoxy resin, available from HEXION company;
EPON826 Resins, epoxy: bisphenol A type epoxy resin, available from HEXION company;
Dicyclohexyl carbodiimide: the wet and heat ageing resistant agent, available from traditional Chinese medicines chemical reagent company limited;
The phenylbenzene carbodiimide: the wet and heat ageing resistant agent, available from traditional Chinese medicines chemical reagent company limited;
The divinyl carbodiimide: the wet and heat ageing resistant agent, available from traditional Chinese medicines chemical reagent company limited;
The diethyl carbodiimide: the wet and heat ageing resistant agent, available from traditional Chinese medicines chemical reagent company limited;
STABAXOL P: polycarbodiimide, available from Rhein Chemie company;
STABAXOL 100P: polycarbodiimide, the wet and heat ageing resistant agent is available from Rhein Chemie company;
STABAXOL 200P: polycarbodiimide, the wet and heat ageing resistant agent is available from Rhein Chemie company;
MX125: the toughness reinforcing bisphenol A epoxide resin of nucleocapsid structure, available from KANEKA company, MX157 and MX257;
MX153: the toughness reinforcing bisphenol A epoxide resin of nucleocapsid structure, available from KANEKA company;
MX157: the toughness reinforcing bisphenol A epoxide resin of nucleocapsid structure, available from KANEKA company;
MX257: the toughness reinforcing bisphenol A epoxide resin of nucleocapsid structure, available from KANEKA company;
Polyethex amine modification epoxy prepolymer: self-control;
EP49-10N: the phosphatization modified epoxy, available from ADEKA company;
NC513: simple function group epoxy reaction type thinner, available from Cardolite company;
Lite 2513HP: simple function group epoxy reaction type thinner, available from Cardolite company;
Wollastonite: commercially available prod;
Calcium sulfate: commercially available prod;
Aerosil: commercially available prod;
Dyhard 100SH: Dyhard RU 100 class solidifying agent, available from Degussa company;
Dyhard 100S: Dyhard RU 100 class solidifying agent, available from Degussa company;
CG-1200: Dyhard RU 100 class solidifying agent, available from Air product company;
CG-1400: Dyhard RU 100 class solidifying agent, available from Air product company;
DDA5: ureas curing catalyst; Available from CVC company;
Dyhard UR200: ureas curing catalyst; Available from Degussa company;
Dyhard UR300: ureas curing catalyst; Available from Degussa company;
Dyhard UR500: ureas curing catalyst; Available from Degussa company;
Dyhard UR700: ureas curing catalyst; Available from Degussa company;
U-52M: ureas curing catalyst; Available from CVC company;
U-405M: ureas curing catalyst; Available from CVC company;
Embodiment 1 preparation single component ageing-resistant epoxy resin binder composition
At first, preparation polyethex amine modification bisphenol A epoxide resin prepolymer: under 25 ℃, 100gEPON828 Resins, epoxy joined 60g polyetheramine (D2000, Huntsman company) in, then add 3g phenyltrimethoxysila,e coupling agent and mix, then with 2 ℃/minutes heating rate with mixture heating up to 80, reacted 2 hours, then continue to be heated to 120 ℃ with 2 ℃ of/minute heating rate, reacted cool to room temperature, discharging 1 hour.
At 50 ℃ with 100g bisphenol A-type Epon828 Resins, epoxy, 300gMX153 nucleocapsid structure modified resin, 107g polyethex amine modification epoxy prepolymer, 120g phosphatization modified bisphenol A epoxy resin EP49-10N mix, stir speed (S.S.) is 800 rev/mins, the time of mixing is 10 minutes, then in said mixture, add 24g NC513 monofunctional epoxy thinner, 150g wollastonite packing, 40g aerosil, with the agent of 8g wet and heat ageing resistant, mix, stir speed (S.S.) is 500 rev/mins, and the time of mixing is 15 minutes.Then mixture is cooled to 25 ℃, adds 49gDyhard100SH Dyhard RU 100 class solidifying agent and 2.5g DyhardUR300 ureas curing catalyst, mix, stir speed (S.S.) is 800 rev/mins, the time of mixing be 10 minutes can be canned.
Embodiment 2～10
According to table 1 ingredients listed and consumption proportion, at 40～50 ℃ liquid bisphenol A epoxide resin, toughness modified bisphenol A type Resins, epoxy, polyethex amine modification epoxy prepolymer, phosphatization modified bisphenol A epoxy resin agitating are mixed, stir speed (S.S.) is 1000 rev/mins, the time of mixing is 10 minutes, then in said mixture, add monofunctional epoxy thinner, filler, thixotropic agent and wet and heat ageing resistant agent, mix, stir speed (S.S.) is 1000 rev/mins, and the time of mixing is 15 minutes.Then mixture is cooled to 25 ℃, adds Dyhard RU 100 class solidifying agent and ureas curing catalyst, mix, stir speed (S.S.) is 1000 rev/mins, and the time of mixing is to get final product in 10 minutes.
The preparation process of the polyethex amine modification epoxy prepolymer that uses among the embodiment 2,3 is: under 25 ℃ 100g bisphenol A epoxide resin Epon828,40g polyetheramine D230,2g phenyltrimethoxysila,e coupling agent are mixed, be heated to 90 ℃, reacted 2 hours, then continue to heat to 130 ℃, reacted 1 hour, after the cooling and get final product.Apply mechanical stirring in the whole preparation process, stir speed (S.S.) is at 1000 rev/mins.
The preparation process of the polyethex amine modification epoxy prepolymer that uses among the embodiment 4,6 is:: under 25 ℃, 100g bisphenol A epoxide resin Epon826,60g polyetheramine T403,2.5g phenyltrimethoxysila,e coupling agent are mixed, be heated to 100 ℃, reacted 2 hours, then continue to heat to 120 ℃, reacted 2 hours, after the cooling and get final product.Apply mechanical stirring in the whole preparation process, stir speed (S.S.) is at 1500 rev/mins.
The preparation process of the polyethex amine modification epoxy prepolymer that uses among the embodiment 5,7,8 is:: under 25 ℃, 100g bisphenol A epoxide resin E44,40g polyetheramine T5000,3g phenyltrimethoxysila,e coupling agent are mixed, be heated to 100 ℃, reacted 1.5 hours, then continue to heat to 120 ℃, reacted 2 hours, after the cooling and get final product.Apply mechanical stirring in the whole preparation process, stir speed (S.S.) is at 2000 rev/mins.
The preparation process of the polyethex amine modification epoxy prepolymer that uses among the embodiment 9,10 is:: under 25 ℃, 100g bisphenol A epoxide resin E51,60g polyetheramine D2000,2g phenyltrimethoxysila,e coupling agent are mixed, be heated to 80 ℃, reacted 2 hours, then continue to heat to 120 ℃, reacted 2 hours, after the cooling and get final product.Apply mechanical stirring in the whole preparation process, stir speed (S.S.) is at 1000 rev/mins.
Table 1
The performance test results
Adopt Pneumatic glue gun that the tackiness agent of embodiment 1-10 preparation is implemented on respectively the position that needs bonding, under the condition of cure under 170 ℃, solidified 30 minutes.
The shearing resistance test is carried out according to ASTM D 3528 standards, 25 ℃ of probe temperatures, test machine is Zwick/Roell Z050, and test rate 10mm/min lists in table 2 according to the room temperature shearing resistance test result of the epoxy construction binder composition of embodiment 1-10 preparation.By as seen from Table 2, take embodiment 1 as example, the room temperature shearing resistance of aging front tackiness agent of the present invention is 32MPa.Shearing resistance after wearing out in 500 hours is 28MPa, and aging rear shearing resistance reached 23MPa in 1000 hours.
Peel strength test carries out according to ASTM D 828 standards, 25 ℃ of probe temperatures, test machine Zwick/Roell Z050, test rate 50mm/min.The T-shaped peel strength test of room temperature according to the epoxy construction binder composition of embodiment 1-10 preparation the results are shown in table 3.By as seen from Table 3, take embodiment 1 as example, the T-shaped stripping strength of room temperature of aging front tackiness agent of the present invention is 11N/mm.T-shaped stripping strength after wearing out in 500 hours is 10N/mm, and aging rear T-shaped stripping strength reached 8.3N/mm in 1000 hours.
Table 2 steel-steel bond shear strength test result
Table 3 steel-steel T-shaped peel strength test result that bonds
Claims (14)
1. single-component epoxy structure binder composition, it comprises:
-at least a unmodified epoxy resin;
-toughness modified epoxy;
-polyethex amine modification epoxy prepolymer;
-contain the wet and heat ageing resistant additive of carbodiimide structure;
-solidifying agent;
-optional the curing catalyst that exists;
-optional phosphatization the modified epoxy that exists; And
One or more of-optional existence are selected from other following components: filler, monofunctional epoxy response type thinner, thixotropic agent and their mixture.
2. the single-component epoxy structure binder composition of claim 1, it comprises:
At least a unmodified epoxy resin of 100 weight parts;
250～400 weight parts or 270-380 weight part toughness modified epoxy;
90-160 weight part or 100～150 weight part polyethex amine modification epoxy prepolymers;
0.5-10 weight part or 0.8-7 weight part contain the wet and heat ageing resistant additive of carbodiimide structure;
20-70 weight part or 25～60 weight part Dyhard RU 100 class solidifying agent;
1.5-3.5 the optional ureas curing catalyst that exists of weight part or 2-3 weight part;
The optional phosphatization modified epoxy that exists of 80-170 weight part or 100～150 weight parts;
The optional filler that exists of 80～220 weight parts or 90-200 weight part;
The optional monofunctional epoxy response type thinner that exists of 10～50 weight parts or 12-40 weight part; And
The optional thixotropic agent that exists of 25～55 weight parts or 30～50 weight parts.
3. claim 1 or 2 single-component epoxy structure binder composition, wherein said at least a unmodified epoxy resin is liquid bisphenol A epoxy resin.
4. the single-component epoxy structure binder composition of one of claim 1-3, wherein said toughness modified epoxy is selected from the bisphenol A type epoxy resin of liquid nitrile rubber modification, with the bisphenol A type epoxy resin of the polymer toughening of nucleocapsid structure, and the mixture of the two.
5. single component wet and heat ageing resistant epoxy structural adhesive composition as claimed in claim 4, the bisphenol A type epoxy resin center of wherein said polymer toughening with nucleocapsid structure is rubber elastomer, shell is polystyrene.
6. the single-component epoxy structure binder composition of one of claim 1-5, wherein the polyethex amine modification epoxy prepolymer is polyetheramine and/or the polyetheramine of number-average molecular weight 2000～5000 and the reaction product of Resins, epoxy of number-average molecular weight 200～400, wherein the weight ratio of the polyetheramine of the polyetheramine of molecular weight 200～400 and molecular weight 2000～5000 is 1: 1～1: 1.3, is preferably 1: 1～1: 1.1.
7. the single-component epoxy structure binder composition of one of claim 1-6, the wherein said wet and heat ageing resistant additive that contains the carbodiimide structure are to be selected from following group one or more: dicyclohexyl carbodiimide, phenylbenzene carbodiimide, divinyl carbodiimide, diethyl carbodiimide, number-average molecular weight are 300～2000 polycarbodiimide and their mixture.
8. the single-component epoxy structure binder composition of one of claim 1-7, wherein said solidifying agent is Dyhard RU 100 class solidifying agent, is preferably Dicyanodiamide or melamine.
9. the single-component epoxy structure binder composition of one of claim 1-8, wherein said phosphatization modified epoxy is the phosphatization Resins, epoxy that per molecule contains 3 or 3 above epoxide groups.
10. the single-component epoxy structure binder composition of one of claim 1-9, wherein said curing catalyst is the ureas curing catalyst, is preferably urea or thiourea.
11. such as the single-component epoxy structure binder composition of one of claim 1-10, wherein, 25 ℃ of viscosity of simple function group epoxy reaction type thinner are 100～300mPa.s.
12. the single-component epoxy structure binder composition such as one of claim 1-11 is characterized in that: described filler is filler fibrous, the micron dimension size.
13. such as the single-component epoxy structure binder composition of one of claim 1-12, wherein said filler is fibrous wollastonite and/or fibrous calcium sulfate.
14. such as the single-component epoxy structure binder composition of one of claim 1-13, wherein said thixotropic agent is aerosil.
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Application publication date: 20130206 |