CN109575859A - Classification solidification heat-resistance type epoxy adhesive and preparation method thereof - Google Patents
Classification solidification heat-resistance type epoxy adhesive and preparation method thereof Download PDFInfo
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- CN109575859A CN109575859A CN201811345773.8A CN201811345773A CN109575859A CN 109575859 A CN109575859 A CN 109575859A CN 201811345773 A CN201811345773 A CN 201811345773A CN 109575859 A CN109575859 A CN 109575859A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of classifications to solidify heat-resistance type epoxy adhesive, by A, two component compositions of B, wherein component A includes following component: bisphenol A type epoxy resin, and more official's specific epoxy diluents pre-process powdered phenol-formaldehyde resin, first silane activates silicon powder, coating phenolic resin quartz sand, other fillers, anti-settling agent；Wherein B component includes following component: modified amine curing agent, and promotor pre-processes powdered phenol-formaldehyde resin, and the second silane activates silicon powder, coating phenolic resin quartz sand, other fillers, anti-settling agent.The present invention combines epoxy-resin systems and phenolic resin system, keeps its easy to operate, and intensity is good, and temperature tolerance is good, can solidify under normal temperature conditions while can all have preferable intensity under room temperature and high temperature.It is mainly used in anchoring adhesive, fire proof construction reinforced glue etc..The present invention further simultaneously discloses this preparation method for being classified and solidifying heat-resistance type epoxy adhesive.
Description
Technical field
The invention belongs to construction structure glue fields.A kind of classification solidification heat-resistance type epoxy adhesive is more specifically said it is,
The invention further relates to the preparation methods that this classification solidifies heat-resistance type epoxy adhesive.It is mainly used in anchoring adhesive, fire prevention knot
Structure reinforced glue etc..
Background technique
Epoxy resin both can have strong operability as a kind of excellent adhesive resin system with normal temperature cure
Feature, while there are the performances such as excellent adhesive strength, excellent weatherability, water resistance, chemicals-resistant.
Epoxy adhesive generally uses under room temperature as a kind of important structural adhesive.It is widely used in building
The stickup of object inner-outer wall stone material, external reinforcement in new and old buildings object are built, the important places such as road and bridge repairing and reinforcing play in the application
Very important effect.These use occasions usually require that adhesive convenient for construction, normal temperature cure.But the ring of normal temperature cure
Oxide structure glue generally just starts to soften at 40~80 DEG C, and just starts to decompose at 200~300 DEG C or so, therefore can only use
In normal temperature condition.And the epoxy glue used at slightly higher temperature, generally requiring high temperature solidification can just meet the requirements, such as phenolic aldehyde ring
Oxygen glue, anhydride-cured epoxy glue etc., these are to be difficult to live use in structural bonding.More in some special circumstances, such as
Bonding reinforcing bar carries out electric welding field or fire occurs for building, so that environment temperature rapid increase, causes structure gluing
Agent performance change, causes the accident.
Conventional fire resistant resin has phenolic resin class, boron bakelite resin class, curing reaction heterocyclic etc. at present, but
These products under normal temperature state mostly be in solid-state, can not room temperature use, be both needed to be solidified at a higher temperature, in room temperature
In engineering, the above kind is not available.
Epoxy systems adhesive solidifies at normal temperature, and the workable adhesive class material under 200 DEG C or more high temperature, mesh
The preceding country temporarily has not seen relevant report.
And phenolic resin not only has preferable adhesive property as a kind of excellent heat-resistance type resin material, it may have
Extraordinary temperature tolerance (200 DEG C or more) still can maintain good performance at a higher temperature, how by epoxy resin with
Phenolic resin is organically combined, and is allowed to solidify under normal temperature conditions while can be all had under room temperature and high temperature
Preferable intensity is the emphasis of this project research.
Summary of the invention
The first object of the present invention is to overcome the shortcoming of above-mentioned existing background technique, and it is solid to provide a kind of classification
Change heat-resistance type epoxy adhesive.Its is easy to operate, and intensity is good, and temperature tolerance is good, can solidify under normal temperature conditions, while in room temperature
With preferable intensity is all had under high temperature.
The second object of the present invention, which is to provide, prepares this method for being classified and solidifying heat-resistance type epoxy adhesive.
The first object of the present invention is reached by following measure: a kind of classification solidification heat-resistance type epoxy adhesive,
By A, two component compositions of B, by weight A:B=3~4:1；It is characterized in that, wherein component A includes following component: bisphenol-A
100 parts of type epoxy resin, 2-5 parts of more official's specific epoxy diluents pre-process powdered phenol-formaldehyde resin 70-110 parts, and the first silane is living
20-50 parts of SiClx micro mist, 100-160 parts of coating phenolic resin quartz sand, other filler 0-50 parts, 2-5 parts of anti-settling agent；Wherein B
Component includes following component: 100 parts of modified amine curing agent, 5-10 parts of promotor, and powdered phenol-formaldehyde resin 70-110 parts of pretreatment, the
Silicon powder 50-100 parts of disilane activation, 100-160 parts of coating phenolic resin quartz sand, other filler 0-50, anti-settling agent 2-8
Part；Dosage is parts by weight,
More official's specific epoxy diluents, be selected from resorcinolformaldehyde resin, glycerin triglycidyl ether,
Castor oil triglycidyl ether；
The pretreatment powdered phenol-formaldehyde resin and laminated quartz sand phenolic resin, with thermoplastic modification phenolic resin
It is made of raw material, the thermoplastic modification phenolic resin is selected from aniline modified phenolic resin, Cardanol Modified PF Resin；
Other fillers are selected from barium sulfate, magnesia, zirconium oxide and titanium dioxide.
In the above-mentioned technical solutions, the described pretreatment powdered phenol-formaldehyde resin the preparation method is as follows: by thermoplastic modification
Phenolic resin, which is heated to 130~150 DEG C, makes its melting, and the methenamine solution that the content that 15% is added while stirring is 33% is made
Curing agent is maintained stir about 10~20 seconds, then pours out fusant, after it is fully cooled, filled using grinding equipment
It point mills obtained powder, is allowed to partial size at 20~40 microns to get to pretreatment powdered phenol-formaldehyde resin；
The coating phenolic resin quartz sand, first will be quartzy the preparation method is as follows: using 100~150 mesh quartz sands
Sand is heated to 130~150 DEG C, and 5% thermoplastic modification phenolic resin is added under agitation, and being then sufficiently stirred keeps it mixed
It closes uniformly, stirs 1~2 minute, the methenamine that the content for being then added 15% while stirring at the same temperature is 33% is molten
Liquid makees curing agent, after being stirred for 10~20 seconds, discharging cooling, and the good quartz sand of overlay film is crushed and processing of being sieved, it obtains
To required coating phenolic resin quartz sand.
In the above-mentioned technical solutions, first silane activation silicon powder is to be covered using silane coupling agent KH-560
The silicon powder that membrane modifying is crossed, mesh number are 200~1000 mesh；The second silane activation silicon powder is using silane coupling agent
KH-550 carries out the silicon powder that overlay film was modified, and mesh number is 200~1000 mesh.
In the above-mentioned technical solutions, the component A includes following component: 100 parts of bisphenol A type epoxy resin, more officials are extraordinary
4-5 parts of epoxide diluent, 100 parts of powdered phenol-formaldehyde resin are pre-processed, the first silane activates silicon powder 30-50 parts, and phenolic resin covers
120 parts of film quartz sand, other filler 0-30 parts, 2-5 parts of anti-settling agent；Wherein B component includes following component: modified amine curing agent
100 parts, 8-10 parts of promotor, 100 parts of powdered phenol-formaldehyde resin are pre-processed, the second silane activates silicon powder 50-80 parts, phenolic resin
120 parts of laminated quartz sand, other filler 0-40 parts, 3-8 parts of anti-settling agent.
In the above-mentioned technical solutions, the modified amine curing agent is selected from phenol aldehyde modified fatty amine, phenol aldehyde modified aliphatic cyclic amine
With modified aromatic amine.
In the above-mentioned technical solutions, the promotor is 2,4,6- tri- (dimethylamino methyl) phenol.
In the above-mentioned technical solutions, the anti-settling agent is selected from fumed silica, organobentonite, talcum powder.
In the above-mentioned technical solutions, the pretreatment powdered phenol-formaldehyde resin adds 100 parts by weight, B component in component A
100 parts by weight of middle addition；The coating phenolic resin quartz sand adds 120 parts by weight in component A, adds 120 in B component
Parts by weight.
In the above-mentioned technical solutions, the component A includes following component: 100 parts of bisphenol A type epoxy resin, more officials are extraordinary
4 parts of epoxide diluent, 100 parts of powdered phenol-formaldehyde resin are pre-processed, the first silane activates 30 parts of silicon powder, coating phenolic resin quartz
120 parts of sand, 30 parts of other fillers, 3 parts of anti-settling agent；Wherein B component includes following component: 100 parts of modified amine curing agent, promotor
8 parts, 100 parts of powdered phenol-formaldehyde resin of pretreatment, 70 parts of silicon powder of the second silane activation, 120 parts of coating phenolic resin quartz sand,
30 parts of its filler, 5 parts of anti-settling agent.
The second object of the present invention is reached by following measure: preparing the classification solidification heat-resistance type Wear Characteristics of Epoxy Adhesive
The method of agent includes the following steps: to put into liquid resin raw material involved in component A in stirred tank, then by other raw materials
And powder is successively put into stirred tank, is sufficiently stirred and is become homogeneous paste object or lotion, and A group finished product is obtained；By B component
In related liquid resin raw material investment stirred tank, then other raw materials and powder are successively put into stirred tank, sufficiently stirred
It mixes and becomes homogeneous paste object or lotion, obtain B group finished product, distribute filling A, B component finished product in proportion.
Technical solution of the present invention can obtain following the utility model has the advantages that (1) present invention point compared with the current prior art
Grade solidification heat-resistance type epoxy adhesive, epoxy-resin systems can organically be integrated, be allowed to both with phenolic resin system
Normal temperature cure with epoxy resin can also release the excellent heat resistance of phenolic resin at high temperature.Relative to general ring
For oxygen glue kind, this system can solidify at normal temperature and reach the strength demand of general structure glue, and when temperature continues
, then can be with further occurrence " second level solidification " when promotion, i.e., at high temperature in very short time, the rear solidification that phenolic resin occurs is anti-
It answers, further provides for the intensity under high temperature for this system.Therefore adhesive of the invention can realize normal temperature cure, make under high temperature
With, further, with system formula adjust, the temperature capacity of this system can be enhanced, or even at extreme temperatures
(300 degree or more), this system adhesive can also have certain intensity.The meaning of such feature is that this adhesive is used for
When structural strengthening, when local environment encounters the extreme conditions such as fire, it can show heat-resisting better than common epoxy structural rubber
Property, enable building to maintain the longer time without collapsing in a fire, strives for more times and machine for people's escape
Meeting.
Detailed description of the invention
Fig. 1 is the mechanical change situation map that the additive amount and this system formula of powdered phenol-formaldehyde resin are pre-processed in the present invention.
Wherein abscissa indicates additive amount, unit: parts by weight；Ordinate indicates intensity, unit: MPa.
Fig. 2 is the mechanical change situation map of the additive amount of coating phenolic resin quartz sand and this system formula in the present invention.
Wherein abscissa indicates additive amount, unit: parts by weight；Ordinate indicates intensity, unit: MPa.
Specific embodiment
The performance that the invention will now be described in detail with reference to the accompanying drawings, but they and do not constitute a limitation of the invention, only
It is for example.Simultaneously by illustrating that advantages of the present invention will become clearer and be readily appreciated that.In addition, disclosed below
Involved technical characteristic can be combined with each other as long as they do not conflict with each other in each embodiment of the present invention, this Shen
Please in dosage be parts by weight.
A kind of classification of the present invention solidifies heat-resistance type epoxy adhesive, and by A, two components of B are formed, by weight A:B=3~
4:1；It is characterized in that, wherein component A includes following component: 100 parts of bisphenol A type epoxy resin, more official's specific epoxy diluents
2-5 parts, powdered phenol-formaldehyde resin 70-110 parts is pre-processed, the first silane activates silicon powder 20-50 parts, coating phenolic resin quartz sand
100-160 parts, other filler 0-50 parts, 2-5 parts of anti-settling agent；Wherein B component includes following component: 100 parts of modified amine curing agent,
5-10 parts of promotor, powdered phenol-formaldehyde resin 70-110 parts is pre-processed, the second silane activates silicon powder 50-100 parts, and phenolic resin covers
100-160 parts of film quartz sand, other filler 0-50,2-8 parts of anti-settling agent；Dosage is parts by weight,
The bisphenol A epoxide resin is the general bisphenol A type epoxy resin of liquid-type, including E-51, E-44；
More official's specific epoxy diluents include but is not limited to resorcinolformaldehyde resin, and glycerine three shrinks
Glycerin ether, castor oil triglycidyl ether；
The pretreatment powdered phenol-formaldehyde resin and laminated quartz sand phenolic resin, with thermoplastic modification phenolic resin
It is made of raw material, the thermoplastic modification phenolic resin includes but is not limited to aniline modified phenolic resin, modified by cardanol phenol
Urea formaldehyde；
Other fillers include but is not limited to barium sulfate, magnesia, zirconium oxide and titanium dioxide.
The described pretreatment powdered phenol-formaldehyde resin the preparation method is as follows:
Thermoplastic modification phenolic resin is placed in flask, being heated to 130~150 DEG C makes its melting, the thermoplasticity
Promotor containing salicylic acid and silane coupling agent (have contained bigcatkin willow in commercially available thermoplastic modification phenolic resin in phenol-formaldehyde resin modified
Sour promotor and silane coupling agent), the methenamine solution that the content that 15% is added while stirring is 33% makees curing agent, maintains
Stir about 10~20 seconds, then fusant is poured out, after it is fully cooled, it is sufficiently milled obtained powder using grinding equipment
End, be allowed to partial size 20~40 microns to get to pretreatment powdered phenol-formaldehyde resin.
The coating phenolic resin quartz sand the preparation method is as follows:
Using 100~150 mesh quartz sands, using sand coating machine, quartz sand is heated to 130~150 DEG C, in stirring bar
5% thermoplastic modification phenolic resin, promotor containing salicylic acid and silicon in the thermoplastic modification phenolic resin are added under part
Alkane coupling agent (has contained salicylic acid promotor and silane coupling agent in commercially available thermoplastic modification phenolic resin), then sufficiently stirs
Mixing is uniformly mixed it, stirs 1~2 minute, the crow that the content for being then added 15% while stirring at the same temperature is 33%
Lip river tropine solution makees curing agent, after being stirred for 10~20 seconds, discharging cooling, and the good quartz sand of overlay film is crushed and is sieved
Processing, obtains required coating phenolic resin quartz sand.
The preferable amount of first silane activation silicon powder and the second silane activation silicon powder in the present invention are as follows: described first
Silane activation silicon powder is that the silicon powder that overlay film was modified is carried out using silane coupling agent KH-560, and mesh number is 200~1000 mesh.
The second silane activation silicon powder is to carry out the silicon powder that overlay film was modified using silane resin acceptor kh-550, and mesh number is
200~1000 mesh.
Preferred embodiment is as follows in the present invention: a kind of classification solidifies heat-resistance type epoxy adhesive, the component A include with
Lower component: 100 parts of bisphenol A type epoxy resin, 4-5 parts of more official's specific epoxy diluents pre-process 100 parts of powdered phenol-formaldehyde resin,
First silane activates silicon powder 30-50 parts, 120 parts of coating phenolic resin quartz sand, other filler 0-30 parts, 2-5 parts of anti-settling agent；
Wherein B component includes following component: 100 parts of modified amine curing agent, 8-10 parts of promotor, 100 parts of powdered phenol-formaldehyde resin are pre-processed,
Second silane activates silicon powder 50-80 parts, 120 parts of coating phenolic resin quartz sand, other filler 0-40 parts, 3-8 parts of anti-settling agent.
The modified amine curing agent is selected from phenol aldehyde modified fatty amine, phenol aldehyde modified aliphatic cyclic amine and modified aromatic amine.
The promotor is 2,4,6- tri- (dimethylamino methyl) phenol, i.e. DMP-30.
The anti-settling agent includes but is not limited to fumed silica, organobentonite, talcum powder.
It is as follows that the present invention is classified preferred embodiment in solidification heat-resistance type epoxy adhesive: the component A includes following
Component: 100 parts of bisphenol A type epoxy resin, more 4 parts of official's specific epoxy diluent, 100 parts of powdered phenol-formaldehyde resin of pretreatment, first
30 parts of silicon powder of silane activation, 120 parts of coating phenolic resin quartz sand, 30 parts of other fillers, 3 parts of anti-settling agent；The B component packet
Containing following component: 100 parts of modified amine curing agent, 8 parts of promotor, pre-processing 100 parts of powdered phenol-formaldehyde resin, the second silane activates silicon
70 parts of micro mist, 120 parts of coating phenolic resin quartz sand, 30 parts of other fillers, 5 parts of anti-settling agent (embodiment of the present invention 9).
The method for being classified and solidifying heat-resistance type epoxy adhesive is prepared, is included the following steps: liquid involved in component A
Body resin raw material is put into stirred tank, is then successively put into stirred tank other raw materials and powder, is sufficiently stirred and becomes
Homogeneous paste object or lotion obtain A group finished product；Liquid resin raw material involved in B component is put into stirred tank, then will
Other raw materials and powder are successively put into stirred tank, are sufficiently stirred and are become homogeneous paste object or lotion, and B composition is obtained
Product distribute filling A, B component finished product in proportion.
Mechanism explanation of the present invention: epoxy adhesive according to the present invention mainly consists of three parts.
First part: for epoxy resin and modified amine curing agent.This part can solidify at normal temperature and obtain preferable
Intensity needed for room temperature, selected modified amine curing agent itself have preferable heat resistance, while to promote heat resistance, diluent
Also use that temperature tolerance is preferable and the higher extraordinary diluent of degree of functionality.
Second part: pretreatment powdered phenol-formaldehyde resin and coating phenolic resin quartz sand.At normal temperature, they are mainly in body
Filler is used as in system, and the phenolic resin composition contained by them has made advanced processing and has fed them into B-stage, works as environment temperature
When further raising reaches 150-200 DEG C, they (several seconds) can carry out reaction solidification in a very short period of time, generate heat resistance pole
Good thermosetting property adhesive material, that is, phenolic resin C-stage, so that system is effectively bonded at high temperature.Part phenol is also had simultaneously
Urea formaldehyde and epoxy resin carry out cross-linking reaction, further improve system intensity.
The A of phenolic resin, B, C three phases represent three kinds of different curing degrees of phenolic resin.The A stage indicates resin
For the complete thermoplastic sexual stage, heat it is fusible, it is cooling then as solid-state.B-stage indicates resin by preliminary with curing agent
Reaction, there is a degree of crosslinking, but not reaction completely, still there is certain bonding stickiness.C-stage indicates that resin is full cross-linked solid
Change, becomes not melt the thermosetting kenel that do not melt.
Part III: other fillers include that heat-resistance type filler (includes but are not limited to barium sulfate, zirconium oxide, titanium dioxide
Deng), modified filler (such as silane-modified activation silicon powder) and anti-settling agent (fumed silica is included but are not limited to, it is organic
Bentonite, talcum powder).Their effect is increase system intensity, heat resistance and storage stability.Wherein modified filler institute
The relationship in gradient of mesh number used in the mesh number and overlay film quartz sand of selection, can play the role of gradation in system, can be further
The intensity of promotion system.
When under normal temperature environment, this system adhesive strength is mainly provided by epoxy resin solidifying system, pre-processes phenolic aldehyde
Resin and coating phenolic resin quartz sand only make filler in system.After environment temperature increases, phenolic resin solidifies rapidly, and
Epoxy systems can soften, then system adhesive strength substitutes epoxy resin by phenolic resin to provide.Meanwhile epoxy and phenolic aldehyde
Fully dispersed, the two forms interpenetrating networks, and epoxy then plays the role of toughening in system.
The transition of first part to second part is extremely important in the present invention, overlong time, then when the temperature rises, glue
Stick system can fail within the two-part transitional period, thus can not continued adhesion.Therefore, it is necessary to before first part fails,
Second part, which is rapidly completed, to be solidified and reaches applicable intensity.The epoxy curing systems of heat-resistance type are consolidated with quick in the present invention system
The combination of the phenolic system of change preferably resolves this problem.
The present invention is classified solidification heat-resistance type epoxy adhesive, is mainly used as the use of the structure glues such as bar planting, anchoring, it is also possible to make
Other bondings use and (need to carry out relevant item detection before use).This adhesive meets following technical indicator:
| Room temperature | 200 DEG C of processing | 300 DEG C of processing | |
| Compression shear strength, MPa | ≥15 | ≥10 | -- |
| Drawing adhesive strength, MPa | ≥11 | ≥8.5 | ≥5 |
Compression shear strength: by 6.3.4 test in GB/T 547-1994, stone material selects Shanxi black granite, having a size of 50mm ×
30mm × 20mm, splicing area are 50mm × 20mm.After conserving 7 days at normal temperature, the test of room temperature compression shear, 200 DEG C are carried out respectively
Compression shear that treated test.
Drawing adhesive strength: drawing property test is carried out according to GB50728-2011 standard requirements, detection method is referring to (attached
Record the adhesion strength measuring method of adhesive bonds reinforcing bar and substrate concrete under K constraint drawing condition).Using C30 concrete,
The screw-thread steel of diameter phi 25mm, punching depth are 150mm.After conserving 7 days at normal temperature, room temperature pull-out test, 200 are carried out respectively
Treated the pull-out test of DEG C treated pull-out test and 300 DEG C.
The wherein performance test of " 200 DEG C of processing " and " 300 DEG C of processing " is to handle test specimen 30min at the corresponding temperature
Afterwards, mechanical test is carried out while hot at once.
The determination of the additive amount range of powdered phenol-formaldehyde resin is pre-processed in the present invention
Abscissa indicates that additive amount, ordinate indicate compression shear strength in Fig. 1；Fig. 1 shows pretreatment powdered phenol-formaldehyde resins
The situation of change of mechanics when additive amount is formulated room temperature mechanics and 200 DEG C to this system.It can be seen that according to Fig. 1 when pretreatment powdery
When the additive amount of phenolic resin is stepped up, mechanical strength is gradually reduced under invention adhesive room temperature；And compression shear at 200 DEG C
Intensity is gradually promoted.This is because bulk strength is relatively low, therefore additive amount is got over when pretreatment powdered phenol-formaldehyde resin is as filler
More, adhesive intensity can be declined under room temperature；And at high temperature, pretreatment phenolic resin will provide under high temperature needed for it is strong
Degree, therefore content increase helps to improve high temperature strength.For the performance under balance room temperature and high temperature, the present invention pre-processes powdery phenol
The additive amount of urea formaldehyde determines are as follows: additive amount is 70~110 parts by weight.
The determination of the additive amount range of coating phenolic resin quartz sand in the present invention
Fig. 2 abscissa indicates that additive amount, ordinate indicate compression shear strength.Fig. 2 indicates adding for coating phenolic resin quartz sand
The situation of change of mechanics when dosage is formulated room temperature mechanics and 200 DEG C to this system.It can be seen that according to chart, work as coating phenolic resin
When the additive amount of quartz sand is stepped up, mechanical strength is gradually reduced under invention adhesive room temperature, and compression shear at 200 DEG C is strong
Degree is in downward trend after first rising.This is because coating phenolic resin quartz sand is as filler, additive amount is more, solid-to-liquid ratio by
Step increases, and adhesive intensity can be declined under room temperature；And at high temperature, coating phenolic resin quartz sand also can be with pretreatment powder
Shape phenolic resin is crosslinked together, the intensity needed for providing under high temperature, therefore content increase helps to improve high temperature strength, and is worked as and contained
When measuring excessively high, and will cause amount of filler excessively makes system adhesive property tend to decline.For the performance under balance room temperature and high temperature
And influenced caused by solid-to-liquid ratio, the additive amount of coating phenolic resin quartz sand determines are as follows: additive amount is 100~160 parts by weight.
Meanwhile when pretreatment powdered phenol-formaldehyde resin additive amount is 100 parts by weight, coating phenolic resin quartz sand additive amount is
When 120 parts by weight, comprehensive performance is best.
Specific embodiment
The component and proportion table that table 1 is embodiment 1-6
The component and proportion table that table 2 is embodiment 7-12
The component and proportion table that table 3 is embodiment 13-18
Table 4 is the detection data table of 1-18 of the embodiment of the present invention and comparative example:
Wherein comparative example selects market brand anchoring adhesive.
From the point of view of comprehensive performance, wherein embodiment 2,8,9,17 be preferred embodiment, and wherein embodiment 9 is best implements
Example.
Other unspecified parts are the prior art.
Claims (10)
1. a kind of classification solidifies heat-resistance type epoxy adhesive, by A, two component compositions of B, by weight A:B=3~4:1；It is special
Sign is that wherein component A includes following component: 100 parts of bisphenol A type epoxy resin, 2-5 parts of more official's specific epoxy diluents, in advance
Powdered phenol-formaldehyde resin 70-110 parts of processing, the first silane activate silicon powder 20-50 parts, coating phenolic resin quartz sand 100-160
Part, other filler 0-50 parts, 2-5 parts of anti-settling agent；Wherein B component includes following component: 100 parts of modified amine curing agent, promotor
5-10 parts, powdered phenol-formaldehyde resin 70-110 parts is pre-processed, the second silane activates silicon powder 50-100 parts, coating phenolic resin quartz
100-160 parts of sand, other filler 0-50,2-8 parts of anti-settling agent；Dosage is parts by weight,
More official's specific epoxy diluents are selected from resorcinolformaldehyde resin, glycerin triglycidyl ether, castor-oil plant
Oily triglycidyl ether；
The pretreatment powdered phenol-formaldehyde resin and laminated quartz sand phenolic resin is original with thermoplastic modification phenolic resin
Material is made, and the thermoplastic modification phenolic resin is selected from aniline modified phenolic resin, Cardanol Modified PF Resin；
Other fillers are selected from barium sulfate, magnesia, zirconium oxide and titanium dioxide.
2. a kind of classification according to claim 1 solidifies heat-resistance type epoxy adhesive, it is characterised in that the pretreatment
Powdered phenol-formaldehyde resin the preparation method is as follows: thermoplastic modification phenolic resin, which is heated to 130~150 DEG C, makes its melting, while stirring
The methenamine solution that the content for mixing side addition 15% is 33% makees curing agent, maintains stir about 10~20 seconds, then will melting
Object is poured out, and after it is fully cooled, it is sufficiently milled obtained powder using grinding equipment, is allowed to partial size at 20~40 microns,
Obtain pretreatment powdered phenol-formaldehyde resin；
The coating phenolic resin quartz sand is first added quartz sand the preparation method is as follows: using 100~150 mesh quartz sands
5% thermoplastic modification phenolic resin is added to 130~150 DEG C in heat under agitation, and being then sufficiently stirred keeps its mixing equal
It is even, it stirs 1~2 minute, the methenamine solution that the content for being then added 15% while stirring at the same temperature is 33% is made
Curing agent, after being stirred for 10~20 seconds, discharging cooling, and the good quartz sand of overlay film is crushed and processing of being sieved, obtain institute
The coating phenolic resin quartz sand needed.
3. a kind of classification according to claim 1 or 2 solidifies heat-resistance type epoxy adhesive, it is characterised in that described first
Silane activation silicon powder is that the silicon powder that overlay film was modified is carried out using silane coupling agent KH-560, and mesh number is 200~1000 mesh；
The second silane activation silicon powder is to carry out the silicon powder that overlay film was modified using silane resin acceptor kh-550, and mesh number is
200~1000 mesh.
4. a kind of classification according to claim 1 or 2 solidifies heat-resistance type epoxy adhesive, it is characterised in that the component A
Include following component: 100 parts of bisphenol A type epoxy resin, 4-5 parts of more official's specific epoxy diluents pre-process powdered phenol-formaldehyde resin
100 parts, silicon powder 30-50 parts of the first silane activation, 120 parts of coating phenolic resin quartz sand, other filler 0-30 parts, anti-settling agent
2-5 parts；Wherein B component includes following component: 100 parts of modified amine curing agent, 8-10 parts of promotor, pre-processing powdered phenol-formaldehyde resin
100 parts, silicon powder 50-80 parts of the second silane activation, 120 parts of coating phenolic resin quartz sand, other filler 0-40 parts, anti-settling agent
3-8 parts.
5. a kind of classification according to claim 4 solidifies heat-resistance type epoxy adhesive, it is characterised in that the modified amine
Curing agent is selected from phenol aldehyde modified fatty amine, phenol aldehyde modified aliphatic cyclic amine and modified aromatic amine.
6. a kind of classification according to claim 5 solidifies heat-resistance type epoxy adhesive, it is characterised in that the promotor
For 2,4,6- tri- (dimethylamino methyl) phenol.
7. a kind of classification according to claim 6 solidifies heat-resistance type epoxy adhesive, it is characterised in that the anti-settling agent
Selected from fumed silica, organobentonite, talcum powder.
8. a kind of classification according to claim 1 or 2 solidifies heat-resistance type epoxy adhesive, it is characterised in that the pre- place
Powdered phenol-formaldehyde resin is managed, 100 parts by weight is added in component A, 100 parts by weight is added in B component；The coating phenolic resin stone
Sand adds 120 parts by weight in component A, 120 parts by weight is added in B component.
9. a kind of classification according to claim 4 solidifies heat-resistance type epoxy adhesive, it is characterised in that the component A includes
Following component:, more 4 parts of official's specific epoxy diluent, pre-processing 100 parts of powdered phenol-formaldehyde resin by 100 parts of bisphenol A type epoxy resin,
30 parts of silicon powder of first silane activation, 120 parts of coating phenolic resin quartz sand, 30 parts of other fillers, 3 parts of anti-settling agent；Wherein B group
Part includes following component: 100 parts of modified amine curing agent, 8 parts of promotor, pre-processing 100 parts of powdered phenol-formaldehyde resin, the second silane is living
70 parts of SiClx micro mist, 120 parts of coating phenolic resin quartz sand, 30 parts of other fillers, 5 parts of anti-settling agent.
10. classification described in any claim solidifies the method for heat-resistance type epoxy adhesive, feature in preparation claim 1-9
It is to include the following steps: to put into liquid resin raw material involved in component A in stirred tank, then by other raw materials and powder
It successively puts into stirred tank, is sufficiently stirred and becomes homogeneous paste object or lotion, obtain A group finished product；It will be involved by B component
Liquid resin raw material investment stirred tank in, then other raw materials and powder are successively put into stirred tank, being sufficiently stirred makes it
As homogeneous paste object or lotion, B group finished product is obtained, distributes filling A, B component finished product in proportion.
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Effective date of registration: 20230828 Address after: No. 6 Danjin Road, Industrial Concentration Zone, Baita Town, Jintan District, Changzhou City, Jiangsu Province, 213299 Patentee after: Jiangsu Hercules Marble Care Materials Co.,Ltd. Address before: 430040 No.26, Jinhai Industrial Park Road, Jinyinhu office, Dongxihu District, Wuhan City, Hubei Province Patentee before: WUHAN KEDA MARBLE PROTECTIVE MATERIALS Co.,Ltd. |
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