CN104004483A - Impact-resistant, high-flexibility and high-temperature-resistant epoxy adhesive and preparation process thereof - Google Patents

Abstract

The invention discloses an impact-resistant, high-flexibility and high-temperature-resistant epoxy adhesive which comprises a component A and a component B, wherein the component A comprises a matrix formed by mixing bisphenol A with 4,4-diaminodiphenylmethane tetraglycidylamine resin according to a weight ratio of 70:30, a flexibilizer, a coupler KH560 and aluminum oxide filler; the component B comprises reactive polyamide resin synthesized from dimer fatty acid and polyamine, a modified high-temperature-resistant fatty amine curing agent, ATBN (amine terminated liquid nitrile-butadiene rubber), a coupler KH550 and aluminum oxide filler. According to the epoxy adhesive, the flexibility is improved to the maximum extent and the shear stripping strength and the impact-resistance strength are improved under the circumstance that high Tg temperature is ensured; the epoxy adhesive has relatively high glass-transition temperature and impact strength. Compared with a conventional high-temperature-resistant adhesive, the epoxy adhesive is relatively good in flexibility and impact resistance. Compared with most of flexibilizing epoxy adhesives, the high-temperature strength of the epoxy adhesive is remarkably enhanced. The strength of the epoxy adhesive still can reach 15-20Mpa at 120 DEG C.

Description

Shock-resistant, high tenacity, the agent of fire resistant epoxy gluing and manufacture craft thereof

Technical field

The present invention relates to sizing agent, especially relate to the high temperature resistant and toughness reinforcing applied research of epoxy resin, for impact and toughness, have requirement and be heated for a long time the epoxy adhesive that uses and the research of manufacture craft thereof under 120 ℃ of left and right and above environment.

Background technology

The good toughness of the resistant to elevated temperatures general shortage of existing sizing agent, is absorbed in the toughness reinforcing high temperature tolerance that often do not have, and selects fire resistant resin and bisphenol a resin mix to improve temperature tolerance and improve manufacturability in the present invention; Select the high nucleocapsid structure particle good with epoxy consistency of a kind of surperficial ester group content to prepare toughner and coordinate ATBN(amino terminated butadiene acrylonitrile rubber) common modified and impact preventing and toughness; Core-Shell Polymer Particles toughening modifying method controllability is stronger, by controlling the size of core-shell particles, can reduce internal stress, raising bonding strength and the shock resistance of EP modified system, toughening modifying effect highly significant.Selecting nucleocapsid structure inner is the rubber of butadiene type, outside is the MMA that ester group content is high, under shock stress effect, the effect of rubber ion generation cavitation, this cavitation effect will significantly improve resistance to impact shock, and this nucleocapsid structure is in very large interpolation degree, can not reduce temperature tolerance, and ATBN can not affect temperature tolerance (addition is crossed conference impact) within the scope of certain interpolation yet, so, ratio how to control both retains high temperature tolerance when can make toughness and shock resistance improve, how to use the mixing of reactive polyamide resin and high temperature resistant solidifying agent to guarantee that toughness and resistant to elevated temperatures double-deck requirement are the contents that this patent is discussed simultaneously.

Summary of the invention

The object of the invention is to propose a kind of can life-time service temperature 120 ℃ of left and right or more than, bonding strength, toughness and shock resistance are had again the epoxy adhesive of very high requirement simultaneously.

In order to realize object of the present invention, following technical scheme is proposed:

Shock-resistant, high tenacity, a resistant to elevated temperatures epoxy adhesive, consist of following A component and B component, wherein,

A component comprises:

Matrix, described matrix is that weight ratio is dihydroxyphenyl propane and 4,4-diaminodiphenylmethane, four epihydric alcohol amine resins of 70:30;

Toughner;

Coupling agent KH560;

Alumina packing;

B component comprises:

Reactive polyamide resin, synthetic by dimer (fatty acid) yl and polyamines; ,

The high temperature resistant fatty amine hardener of modification;

ATBN；

Coupling agent KH550;

Alumina packing.

Further, in described A component:

40 parts of dihydroxyphenyl propanes;

20 parts of 4,4-diaminodiphenylmethane, four epihydric alcohol amine resins;

20 parts of toughner;

3 parts of coupling agent KH560;

22 parts of alumina packings;

In described B component:

30 parts of reactive polyamide resins;

30 parts of the high temperature resistant fatty amine hardeners of modification;

15 parts of ATBN;

4 parts of coupling agent KH550;

21 parts of alumina packings.

The present invention also proposes the manufacture craft of epoxy adhesive:

A component manufacture craft: by 40 parts of bisphenol A epoxide resins and 4,15 parts of 4-diaminodiphenylmethane four epihydric alcohol amine resins, 20 parts of the toughner configuring, coupling agent KH560 is 3 parts, in reactor, open dispersion impeller and planet, planetary rotating speed 25Hz, disperse rotating speed to control to 20Hz, vacuum degree control is at-0.08--0.1Mpa.Stir clear still after 20 minutes and once, the material that do not stir evenly on stirring tank or still wall is cleared up in still, then add 22 parts of resistant to elevated temperatures alumina packings;

Equally in reactor, open dispersion impeller and planet afterwards, planetary rotating speed 25Hz, disperses rotating speed to control to 20Hz, and vacuum degree control is at-0.08--0.1Mpa.Stir after 15 minutes clear still once, then vacuumize with this understanding and stir 10min, after close dispersion, only open planetary rotating speed and be controlled at 10Hz, vacuum tightness is still controlled at-0.08--0.1Mpa and carries out deaeration, after about deaeration 10min, goes out still;

The manufacture craft of B component: 30 parts of the reactive polyamides that dimer (fatty acid) yl and polyamines are synthetic and 30 parts of the high temperature resistant fatty amine hardeners of modification and add ATBN15 part and 4 parts of coupling agent KH550 in reactor, open dispersion impeller and planet, planetary rotating speed 25Hz, disperse rotating speed to control to 20Hz, vacuum degree control is at-0.08--0.1Mpa.Stir clear still after 15 minutes and once, the material that do not stir evenly on stirring tank or still wall is cleared up in still, then add 22 parts of resistant to elevated temperatures alumina packings;

Equally in reactor, open dispersion impeller and planet afterwards, planetary rotating speed 25Hz, disperses rotating speed to control to 20Hz, and vacuum degree control is at-0.08--0.1Mpa.Stir after 15 minutes clear still once, then vacuumize with this understanding after stirring 10min and close dispersion, only open planetary rotating speed and be controlled at 10Hz, vacuum tightness is still controlled at-0.08--0.1Mpa and carries out deaeration, after about deaeration 10min, goes out still.

The manufacture craft of described toughner: 75 parts of bisphenol F epoxy resins, take core as butadiene type rubber, shell is that 25 parts of the nucleocapsid structure anti-impact modifiers of methyl methacrylate are positioned in sealable reactor, under the condition that is filled with nitrogen protection or vacuumizes, with oil bath or water-bath, heat and then open and disperse 30Hz to 80 ℃, planet 30Hz, vacuum degree control stirs at-0.08--0.1Mpa, after stir about 1 hour, drive still and carry out still clearly, to on stirring or wall, not have dissolved part again to clear up in still, then continue to vacuumize in the above conditions stir about 2 hours, until Powdered nucleocapsid structure toughner is all dissolved into the uniform toughner of oyster white, standby, if uniformity coefficient increases churning time not.

Epoxy adhesive of the present invention, guaranteeing, at high Tg temperature, farthest to increase toughness, improves and shears stripping strength and resistance to impact shock; Have and have higher second-order transition temperature and shock strength.Compared good toughness and shock resistance with high-temperature Resistance Adhesives in the past, compared with most of toughness reinforcing epoxy adhesives, hot strength is significantly improved.120 ℃ of intensity still can reach 15 ~ 20Mpa.

Embodiment

For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, the present invention is described in more detail.

The present invention is with bisphenol a resin and 4,4-diaminodiphenylmethane four glycidyl amines are mixed into matrix resin by a certain percentage, toughness reinforcing aspect is with nucleocapsid structure toughner and the dual toughness reinforcing and raising impact resistance of ATBN of preparation, with a kind of reactive polyamide resin, coordinate modified, high temperature resistant fatty amine curing agent and a kind of shock-resistant, the high tenacity forming, resistant to elevated temperatures epoxy adhesive, 120 ℃ of down cut intensity, still have 15～20MPa, and ambient temperature curable manufacturability is convenient

First 1 be the preparation of preparing nucleocapsid structure toughner: adopt the good bisphenol F epoxy resin 75g of the lower consistency of viscosity; (core is butadiene type rubber to nucleocapsid structure anti-impact modifier; shell is methyl methacrylate) 25g is under nitrogen protection or the condition that vacuumizes; in 80 ℃ of strong stirrings until Powdered nucleocapsid structure toughner is all dissolved into the uniform toughner of oyster white; standby, if uniformity coefficient increases churning time not.

2:AB two component epoxy glueds joint to get off the test that needs are prepared:

15 parts of 40 parts of the main bisphenol A epoxide resins of A component matrix and 4,4-diaminodiphenylmethane, four epihydric alcohol amine resins mix, and add 20 parts of the toughner that configure simultaneously, and add coupling agent KH560(3 part) and 22 parts of resistant to elevated temperatures alumina packings

B component is by 30 parts of the high temperature resistant fatty amine hardeners of dimer (fatty acid) yl and synthetic 30 parts of the reactive polyamides of polyamines and modification and add ATBN15 part and coupling agent KH550(4 part) and 21 parts of resistant to elevated temperatures alumina packings form.

3 design experiments are as follows: (and testing data)

Tackiness agent shearing impact Strength Testing Methods (with reference to GB/T 6328-1999)

Shear strength test method (with reference to GB/T7124-2008)

Peeling strength test method (with reference to GB/T 2791-1995)

The impact of toughner umber proportionings different from ATBN umber on Tg and intensity and shock resistance, wherein,

?	A component	?	B component
				A1	Do not add nucleocapsid toughner	B1	Do not add ATBN
A2	Add 10 parts of nucleocapsid toughner	B2	Add 10 parts of ATBN
				A3	Add 15 parts of nucleocapsid toughner	B3	Add 15 parts of ATBN
A4	Add 20 parts of nucleocapsid toughner	B4	Add 20 parts of ATBN
				A5	Add 30 parts of nucleocapsid toughner	B5	Add 30 parts of ATBN

Under following proportioning, after solidifying respectively, (23 ± 2 ℃ solidify the 100 ℃ of 2h that heat after a day) tests relevant performance

Through 25 mutual experiments, result is:

A1B1: Tg is up to 113 ℃ of its residual strengths and is minimum, shears 22MPa, peels off 2.2N/mm, impacts: 20KJ/M2

90 ℃ of stripping strengths of A5B5:Tg lowest order are up to 6.6N/mm and shear 28MPa, impact: 27 KJ/M2

A4B3: be that wherein over-all properties is best, 108 ℃ of Tg, shear 29MPa, impact 30 KJ/M2 and peel off 5.6N/mm

Wherein A4B3 is 16MPa the shearing resistance of 120 ℃, under 120 ℃ of conditions, places after 1 month digestion time, still has 15.8MPa, can meet the requirement of using at this temperature for a long time

Nucleocapsid structure toughner and ATBN are that to increase toughness better along with addition to epoxy adhesive toughness reinforcing, but this nucleocapsid structure toughner of thermotolerance is to arrive after a certain amount of to start to decline, and ATBN is along with addition increase is linear decline relation substantially.

At the nucleocapsid structure toughner of preparation and the umber of ATBN, respectively in 20 parts and 15 parts, curing system can show best shearing resistance, stripping strength, and the resistance to impact shock while can keep higher second-order transition temperature again.

Although the present invention is own, with preferred embodiment openly as above they are not for limiting the present invention, and the content that protection scope of the present invention should be defined with the application's claim protection domain is as the criterion.Anyly have the knack of the art person, without departing from the spirit and scope of the present invention, various variations of doing or be equal to replacement, all should belong to protection scope of the present invention.

Claims (4)

1. shock-resistant, high tenacity, a resistant to elevated temperatures epoxy adhesive, is characterized in that consisting of following A component and B component, wherein,

A component comprises:

Matrix, described matrix is that weight ratio is dihydroxyphenyl propane and 4,4-diaminodiphenylmethane, four epihydric alcohol amine resins of 70:30;

Toughner;

Coupling agent KH560;

Alumina packing;

B component comprises:

Reactive polyamide resin, synthetic by dimer (fatty acid) yl and polyamines; ,

The high temperature resistant fatty amine hardener of modification;

ATBN；

Coupling agent KH550;

Alumina packing.

2. epoxy adhesive according to claim 1, is characterized in that,

In described A component:

40 parts of dihydroxyphenyl propanes;

20 parts of 4,4-diaminodiphenylmethane, four epihydric alcohol amine resins;

20 parts of toughner;

3 parts of coupling agent KH560;

22 parts of alumina packings;

In described B component:

30 parts of reactive polyamide resins;

30 parts of the high temperature resistant fatty amine hardeners of modification;

15 parts of ATBN;

4 parts of coupling agent KH550;

21 parts of alumina packings.

3. the manufacture craft of epoxy adhesive as claimed in claim 1 or 2, is characterized in that:

A component manufacture craft: by 40 parts of bisphenol A epoxide resins and 4,15 parts of 4-diaminodiphenylmethane four epihydric alcohol amine resins, 20 parts of the toughner configuring, coupling agent KH560 is 3 parts, in reactor, open dispersion impeller and planet, planetary rotating speed 25Hz, disperse rotating speed to control to 20Hz, vacuum degree control is at-0.08--0.1Mpa;

Stir clear still after 20 minutes and once, the material that do not stir evenly on stirring tank or still wall is cleared up in still, then add 22 parts of resistant to elevated temperatures alumina packings;

Equally in reactor, open dispersion impeller and planet afterwards, planetary rotating speed 25Hz, disperses rotating speed to control to 20Hz, and vacuum degree control is at-0.08--0.1Mpa;

Stir after 15 minutes clear still once, then vacuumize with this understanding and stir 10min, after close dispersion, only open planetary rotating speed and be controlled at 10Hz, vacuum tightness is still controlled at-0.08--0.1Mpa and carries out deaeration, after about deaeration 10min, goes out still;

The manufacture craft of B component:

30 parts of the reactive polyamides that dimer (fatty acid) yl and polyamines are synthetic and 30 parts of the high temperature resistant fatty amine hardeners of modification and add ATBN15 part and 4 parts of coupling agent KH550 in reactor, open dispersion impeller and planet, planetary rotating speed 25Hz, disperse rotating speed to control to 20Hz, vacuum degree control is at-0.08--0.1Mpa;

?stir clear still after 15 minutes and once, the material that do not stir evenly on stirring tank or still wall is cleared up in still, then add 22 parts of resistant to elevated temperatures alumina packings;

Equally in reactor, open dispersion impeller and planet afterwards, planetary rotating speed 25Hz, disperses rotating speed to control to 20Hz, and vacuum degree control is at-0.08--0.1Mpa;

Stir after 15 minutes clear still once, then vacuumize with this understanding after stirring 10min and close dispersion, only open planetary rotating speed and be controlled at 10Hz, vacuum tightness is still controlled at-0.08--0.1Mpa and carries out deaeration, after about deaeration 10min, goes out still.

4. the manufacture craft of epoxy adhesive according to claim 3, is characterized in that,

The manufacture craft of described toughner: 75 parts of bisphenol F epoxy resins, take core as butadiene type rubber, shell is that 25 parts of the nucleocapsid structure anti-impact modifiers of methyl methacrylate are positioned in sealable reactor, under the condition that is filled with nitrogen protection or vacuumizes, with oil bath or water-bath, heat and then open and disperse 30Hz to 80 ℃, planet 30Hz, vacuum degree control stirs at-0.08--0.1Mpa, after stir about 1 hour, drive still and carry out still clearly, to on stirring or wall, not have dissolved part again to clear up in still, then continue to vacuumize in the above conditions stir about 2 hours, until Powdered nucleocapsid structure toughner is all dissolved into the uniform toughner of oyster white, standby, if uniformity coefficient increases churning time not.