CN109593512A - Bisphenol type epoxy organic siliconresin and preparation method, adhesive and preparation method - Google Patents
Bisphenol type epoxy organic siliconresin and preparation method, adhesive and preparation method Download PDFInfo
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- CN109593512A CN109593512A CN201810660480.2A CN201810660480A CN109593512A CN 109593512 A CN109593512 A CN 109593512A CN 201810660480 A CN201810660480 A CN 201810660480A CN 109593512 A CN109593512 A CN 109593512A
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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
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- 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
- C09J11/06—Non-macromolecular additives organic
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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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- Inorganic Chemistry (AREA)
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- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of bisphenol type epoxy organic siliconresin, including component A, component B, component C, component D, component A is methyltriethoxysilane or diethoxy methoxy methyl base silane, component B is one ethyl diethoxy silane of dimethyl diethoxysilane or monomethyl, component C is ethyl triethoxysilane or methyltriethoxysilane, and component D is bisphenol A type epoxy resin.The present invention also provides a kind of preparation methods of bisphenol type epoxy organic siliconresin.The present invention also provides a kind of bisphenol type epoxy organic silicon resin adhesives.The present invention also provides a kind of preparation methods of bisphenol type epoxy organic silicon resin adhesive.The beneficial effects of the present invention are: with organosilicon polymer come modified epoxy, it is crisp to substantially improve asphalt mixtures modified by epoxy resin lipid, and impact resistance, the disadvantages of humidity resistance is poor, the internal stress after reducing epoxy resin cure has many advantages, such as that intensity is big, water resistance is good.
Description
Technical field
The present invention relates to painting field more particularly to a kind of bisphenol type epoxy organic siliconresin and preparation methods, one
Kind bisphenol type epoxy organic silicon resin adhesive and preparation method.
Background technique
Epoxy resin has very various excellent performances, such as good mechanical performance, electrical insulation capability, preferable chemistry
Stability, corrosion-resistant, mould proof, solidification temperature range is wide, and crosslink density is easily controllable, and solidification process does not generate small molecule by-product
Object, thus shrinking percentage is low, is based on above-described good service performance, becomes the common production adhesive of one kind, coating
Matrix resin, be widely used in automobile, aviation, machinery, chemical industry and large hydraulic engineering and civil construction industry.
Epoxy resin has above-mentioned many excellent properties, but it still has shortcoming, and if internal stress is big after solidifying, matter is crisp, resistance to
Fatigability, impact resistance, humidity resistance are poor, greatly limit it in the application of certain high-tech sectors.
In recent years, with the rapid development of social economy, structural bond material, encapsulating material, protection and patching material etc.
High performance require epoxy resin have higher performance, such as good toughness, internal stress is low, water resistance etc..
In addition, the construction of off-shore structure and hydraulic engineering make rapid progress, building by water erosion or other it is external because
The infringement of element, causes concrete component surface layer to fall off and damage；The destruction that the positions such as dock, tunnel, underground garage occur is often
It needs to carry out repairing and reinforcing in moist even underwater environment.In addition to this, in daily life, the humidities such as toilet, bathroom
The bonding of environment, repairing, and protection and patching material energy are also required in wet weather, the outdoor repairing and reinforcing in overcast and rainy season etc.
It is enough to be applied under band water environment.
Therefore, the performance of epoxy resin how is improved, and then widens its application range, becomes domestic and international researcher and is badly in need of solution
Certainly the technical issues of.
Summary of the invention
One of the technical problems to be solved by the present invention are: to solve above-mentioned technical problem, a kind of bisphenol type epoxy is provided
Organic siliconresin and preparation method, while a kind of bisphenol type epoxy organic silicon resin adhesive and preparation method being also provided.
The technical scheme adopted by the invention is that:
The present invention provides a kind of bisphenol type epoxy organic siliconresin, including component A, component B, component C, component D, the component A
For methyltriethoxysilane or diethoxy methoxy methyl base silane, the component B is dimethyl diethoxysilane or one
One ethyl diethoxy silane of methyl, the component C are ethyl triethoxysilane or methyltriethoxysilane, the component
D is bisphenol-A type epoxy resin.
The structural formula of component A is
, R can be ethyl, methyl
When R is ethyl, component A is methyltriethoxysilane；When R is methyl, component A is diethoxy methoxy silicon
Alkane.
The structural formula of component B is
, R can be methyl, ethyl
When R is methyl, component B is dimethyl diethoxysilane；When R is ethyl, component B is one ethyl diethoxy of monomethyl
Silane.
The structural formula of component C is
, R can be methyl, ethyl
When R is methyl, component C is ethyl triethoxysilane；When R is ethyl, component C is methyltriethoxysilane.
Component D is bisphenol-A type epoxy resin, be one of bisphenol-A type epoxy resin E20, E44, E51, E12 or
The mixture that the two arbitrarily matches.
In a preferred embodiment of the invention, bisphenol type epoxy organic siliconresin includes methyltriethoxysilane
60g, dimethyl diethoxysilane 60g and ethyl triethoxysilane 20g, bisphenol-A type epoxy resin 100g.
In a preferred embodiment of the invention, bisphenol type epoxy organic siliconresin includes methyltriethoxysilane
20g, dimethyl diethoxysilane 60g and ethyl triethoxysilane 60g, bisphenol-A type epoxy resin 150g.
In a preferred embodiment of the invention, bisphenol type epoxy organic siliconresin includes methyltriethoxysilane
60g, dimethyl diethoxysilane 20g and ethyl triethoxysilane 60g, bisphenol-A type epoxy resin 200g.
The present invention provides a kind of preparation method of bisphenol type epoxy organic siliconresin, and steps are as follows:
1) use organoalkoxysilane for raw material, organoalkoxysilane prepares organosilicon by hydrolytie polycondensation
Oligomer, the organoalkoxysilane include component A, component B, component C, and the component A is methyltriethoxy silane
Alkane or diethoxy methoxy methyl base silane, the component B are one ethyl diethoxy of dimethyl diethoxysilane or monomethyl
Base silane, the component C are ethyl triethoxysilane or methyltriethoxysilane；
Siloxanes hydrolysis condensation reaction equation:
2) secondary hydroxyl of the silicone oligomer of step 1) preparation and bisphenol A type epoxy resin is reacted, forms bisphenol type epoxy
Organic siliconresin.
The reaction equation of silicone oligomer and bisphenol A type epoxy resin:
In a preferred embodiment of the invention,
Above-mentioned steps 1) specific step is as follows: having thermometer, addition funnel, reflux condenser, four mouthfuls of agitating device
In flask, it is packed into dimethylbenzene 100g, is passed through under nitrogen protection, methyltriethoxysilane 60g, dimethyl diethoxy silicon is added
Deionized water 5g is added dropwise after mixing evenly in alkane 60g and ethyl triethoxysilane 20g, is added dropwise 2mol/L's after water is added dropwise
Then hydrochloric acid 0.5g is stirred to liquid-transparent, be warming up to 80 DEG C, is kept temperature 2h heat preservation, is cooled to room temperature after 2h, is evaporated under reduced pressure
Stop being passed through nitrogen afterwards, obtained condensation resin is stored in closed container.
Above-mentioned steps 2) specific step is as follows: by the bisphenol A type epoxy resin of 100g, 50g silicone oligomer and 20g
Cyclohexanone, which is added, is equipped with blender, thermometer, in the four-hole boiling flask of reflux condenser and oil water separator, to epoxy resin whole
Catalyst is added after fusing, is stirred and heated to 150 DEG C of back flow reactions, the ethyl alcohol for reacting generation is removed by oil water separator, reaction
To 3h, modifying epoxy resin by organosilicon is made in cooling, filtering, packaging.
In a preferred embodiment of the invention,
Above-mentioned steps 1) specific step is as follows: having thermometer, addition funnel, reflux condenser, four mouthfuls of agitating device
In flask, it is packed into dimethylbenzene 100g, is passed through under nitrogen protection, methyltriethoxysilane 20g, dimethyl diethoxy silicon is added
Deionized water 4g is added dropwise after mixing evenly in alkane 60g and ethyl triethoxysilane 60g, is added dropwise 2mol/L's after water is added dropwise
Then hydrochloric acid 0.4g is stirred to liquid-transparent, be warming up to 90 DEG C, is kept temperature 4h heat preservation, is cooled to room temperature after 4h, is evaporated under reduced pressure
Stop being passed through nitrogen afterwards, obtained condensation resin is stored in closed container.
Above-mentioned steps 2) specific step is as follows: by the bisphenol A type epoxy resin of 150g, 50g silicone oligomer and 30g
Cyclohexanone, which is added, is equipped with blender, thermometer, in the four-hole boiling flask of reflux condenser and oil water separator, to epoxy resin whole
Catalyst is added after fusing, is stirred and heated to 150 DEG C of back flow reactions, the ethyl alcohol for reacting generation is removed by oil water separator, reaction
To 4h, modifying epoxy resin by organosilicon is made in cooling, filtering, packaging.
In a preferred embodiment of the invention,
Above-mentioned steps 1) specific step is as follows: having thermometer, addition funnel, reflux condenser, four mouthfuls of agitating device
In flask, it is packed into dimethylbenzene 100g, is passed through under nitrogen protection, methyltriethoxysilane 60g, dimethyl diethoxy silicon is added
Deionized water 3g is added dropwise after mixing evenly in alkane 20g and ethyl triethoxysilane 60g, is added dropwise 2mol/L's after water is added dropwise
Then hydrochloric acid 0.3g is stirred to liquid-transparent, be warming up to 100 DEG C, keeps temperature 5h heat preservation, room temperature is cooled to after 5h, decompression is steamed
Stop being passed through nitrogen after evaporating, obtained condensation resin is stored in closed container.
Above-mentioned steps 2) specific step is as follows: by the bisphenol A type epoxy resin of 200g, 50g silicone oligomer and 40g
Cyclohexanone, which is added, is equipped with blender, thermometer, in the four-hole boiling flask of reflux condenser and oil water separator, to epoxy resin whole
Catalyst is added after fusing, is stirred and heated to 150 DEG C of back flow reactions, the ethyl alcohol for reacting generation is removed by oil water separator, reaction
To 5h, modifying epoxy resin by organosilicon is made in cooling, filtering, packaging.
The present invention provides a kind of bisphenol type epoxy organic silicon resin adhesive, the bisphenol type epoxy organic siliconresin gluing
The component that agent includes is bisphenol type epoxy organic siliconresin prepared by the above method, hydrophobic type resin material, resting form solidification
Agent, modified amine, special dry promotor, dimethylbenzene, n-butanol, surfactant, filler, wherein the adhesive components are as follows:
In terms of mass parts, 18-24 parts of bisphenol type epoxy organic siliconresin, 5-8 parts of hydrophobic type resin material, latent curing agent 0.1-1
Part, 1-4 parts of modified amine, dry promotor 0.7-5 parts special, 9-16 parts of dimethylbenzene, 9-16 parts of n-butanol, surfactant 0.2-
0.8 part, 40-57 parts of filler.
In a preferred embodiment of that invention, the bisphenol type epoxy organic siliconresin is that above-mentioned homemade organosilicon changes
Property epoxy resin it is one or more.
In a preferred embodiment of the invention, the hydrophobic type resin material is the polysulfide that molecular weight is 800-1300
Rubber, coumarone indene resin, Petropols it is one or more.
In a preferred embodiment of the invention, the latent curing agent is the Aradur 2863-1 of HUNTSMAN.
In a preferred embodiment of the invention, the modified amine is diethylenetriamine, triethylene tetramine, four ethylene five
One of amine, m-phenylene diamine (MPD), hexamethylene diamine are a variety of.
In a preferred embodiment of the invention, the special dry promotor is HUNTSMAN's
Accelerator 2950。
In a preferred embodiment of the invention, the surfactant is perfluorinated nonene oxygroup benzene sulfonic acid sodium salt.
In a preferred embodiment of the invention, the filler is feldspar powder, in aluminium oxide, wollastonite in powder, silica flour
It is one or more.
In a preferred embodiment of the invention, the adhesive components are as follows: in terms of mass parts, bisphenol type epoxy has
20 parts of machine silicone resin, 7 parts of hydrophobic type resin material, 1 part of latent curing agent, 3 parts of modified amine, special 0.8 part of dry promotor,
11 parts of dimethylbenzene, 11 parts of n-butanol, 0.6 part of surfactant, 45.6 parts of filler.
The present invention provides a kind of preparation method of bisphenol type epoxy organic silicon resin adhesive, and preparation step is as follows:
(1) raw material is weighed by said ratio, part dimethylbenzene and part n-butanol is mixed and made into solvent, are first added into solvent
Part bisphenol A-type organosilicon epoxy resin sequentially adds surfactant, filler, hydrophobic type resinous wood after mixing evenly
Material, after being uniformly dispersed, is placed in grinder and grinds, until fineness of grind is less than or equal to 20 microns, ground mill base is set
In clean stirred tank, sequentially add under agitation remaining bisphenol A-type organosilicon epoxy resin, remaining dimethylbenzene and
N-butanol, after mixing evenly, fineness filter and package discharging at 20 microns or less；
(2) modified amine, latent curing agent, special dry promotor are weighed by said ratio, stirred evenly, bag filter takes on
Material；
(3) then stir with paint according to the ratio that quality proportioning is 2:1 by the product of step (1) and by the product of step (2)
Agitating is even up to bisphenol type epoxy organic silicon resin adhesive.
The beneficial effects of the present invention are:
With organosilicon polymer come modified epoxy, it is crisp to substantially improve asphalt mixtures modified by epoxy resin lipid, fatigue durability, impact resistance, resistance to
The disadvantages of humid is poor.Bisphenol type epoxy organic siliconresin have excellent mechanical property, electrical property, flexibility, heat resistance,
Water resistance and adhesive property can be used for the protective coating and insulating materials used under high temperature, high humidity, jump in temperature environment, such as mine
With machinery, electric locomotive, cable connector, underwater units and H grade motor, submersible electric motor coil impregnated material etc., emphasis
Concentrate on semiconductor devices, sealant, moulding material and coating etc..
Bisphenol type epoxy organic silicon resin adhesive is that one kind uses modifying epoxy resin by organosilicon as matrix resin, is adopted
With the cured engineering adhesive of amine curing agent.After modifying epoxy resin by organosilicon adhesive can substantially reduce epoxy resin cure
Internal stress, have many advantages, such as that intensity is big, water resistance is good, can be widely applied to the repairing and reinforcing of building under wet environment with
And the construction of large pool, hydraulic engineering.
Modifying epoxy resin by organosilicon and modifying epoxy resin by organosilicon adhesive preparation method of the invention is simple, former material
To expect that source is wide and simple to be easy to get, preparation cost is cheap, and it is easy to accomplish, and have no toxic side effect, it is safe and reliable.
Specific embodiment
Embodiment 1:
A kind of bisphenol type epoxy organic silicon resin adhesive is provided, including component (in terms of mass parts): bisphenol type epoxy has
20 parts of machine silicone resin, 7 parts of hydrophobic type resin material, 1 part of latent curing agent, 3 parts of modified amine, special 0.8 part of dry promotor,
11 parts of dimethylbenzene, 11 parts of n-butanol, 0.6 part of surfactant, 45.6 parts of filler, wherein the hydrophobic type resin material is molecule
The polysulfide rubber that amount is 1100, the modified amine are diethylenetriamine, and the surfactant is perfluorinated nonene oxygroup benzene sulfonic acid
Sodium.The filler is feldspar powder, aluminium oxide.
Embodiment 2:
A kind of bisphenol type epoxy organic silicon resin adhesive is provided, including component (in terms of mass parts): bisphenol type epoxy has
18 parts of machine silicone resin, 5 parts of hydrophobic type resin material, 0.1 part of latent curing agent, 1 part of modified amine, special dry promotor 0.7
Part, 9 parts of dimethylbenzene, 9 parts of n-butanol, 0.2 part of surfactant, 57 parts of filler, wherein the hydrophobic type resin material is molecule
The polysulfide rubber that amount is 1200, the modified amine are triethylene tetramine, and the surfactant is perfluorinated nonene oxygroup benzene sulfonic acid
Sodium.The filler is feldspar powder, aluminium oxide, wollastonite in powder, silica flour.
Embodiment 3:
A kind of bisphenol type epoxy organic silicon resin adhesive is provided, including component (in terms of mass parts): bisphenol type epoxy has
24 parts of machine silicone resin, 8 parts of hydrophobic type resin material, 1 part of latent curing agent, 4 parts of modified amine, special 5 parts of dry promotor, two
8 parts of toluene, 9.2 parts of n-butanol, 0.8 part of surfactant, 40 parts of filler, wherein the hydrophobic type resin material is that molecular weight is
1300 polysulfide rubber, the modified amine are one of diethylenetriamine, triethylene tetramine, m-phenylene diamine (MPD), hexamethylene diamine or more
Kind, the surfactant is perfluorinated nonene oxygroup benzene sulfonic acid sodium salt.The filler is feldspar powder, silica flour.
Embodiment 4:
A kind of bisphenol type epoxy organic silicon resin adhesive is provided, including component (in terms of mass parts): bisphenol type epoxy has
18 parts of machine silicone resin, 5 parts of hydrophobic type resin material, 0.3 part of latent curing agent, 3 parts of modified amine, it is special it is dry promote 3.3 parts,
14 parts of dimethylbenzene, 16 parts of n-butanol, 0.4 part of surfactant, 40 parts of filler, wherein the hydrophobic type resin material is molecular weight
For 900 polysulfide rubber, the modified amine is diethylenetriamine, triethylene tetramine, tetraethylenepentamine, m-phenylene diamine (MPD), hexamethylene diamine
One of or it is a variety of, the surfactant be perfluorinated nonene oxygroup benzene sulfonic acid sodium salt.The filler be feldspar powder, aluminium oxide,
Wollastonite in powder, silica flour.
Comparative example:
A kind of bisphenol type epoxy organic silicon resin adhesive is provided, including component (in terms of mass parts): bisphenol type epoxy
20 parts of resin, 7 parts of hydrophobic type resin material, 1 part of latent curing agent, 3 parts of modified amine, special dry promotion 0.8 part, dimethylbenzene
11 parts, 11 parts of n-butanol, 0.6 part of surfactant, 45.6 parts of filler, wherein the hydrophobic type resin material is that molecular weight is
1100 polysulfide rubber, the modified amine are diethylenetriamine, and the surfactant is perfluorinated nonene oxygroup benzene sulfonic acid sodium salt.Institute
Stating filler is feldspar powder, aluminium oxide.
Bisphenol type epoxy organic silicon resin adhesive the performance test results:
(1) test method 1
It using high-mark cement block and 2mm thickness Q235 sandblasting steel plate, after soaking water, takes out, placement surface after obvious washmarking without applying
Work implements embodiment 1 --- embodiment 4 and comparative example, and is bonded corresponding cement block and steel plate, steeps after 10min into originally
In water, the pull-out strength of test block is bonded respectively at 7 days, 28 days, test in 84 days.
1 tap water Soak Test data of table
Remarks: the instrument range that pulls open that this experiment uses is 20MPa, and therefore, embodiment 2 and the underwater steel plate of embodiment 3 are viscous
The component values ratio 20MPa of knotting strength is bigger.
(2) test method 2
It is hung on dedicated platform, at Qingdao seawater test site in tide using high-mark cement block and 2mm thickness Q235 sandblasting steel plate
Construction embodiment 1 --- embodiment 4 and comparative example when water is backed off, and it is bonded corresponding cement block and steel plate, after flood tide certainly
It so impregnates, the pull-out strength after test bonds test block 7 days, 28 days respectively in this way.
2 nature seawater Soak Test data of table
(3) test method 3
Installation revolution drum in Acceleration study device is impregnated in manual simulation's seawater, and makes its revolution with motor, adjustment needs to rotate
Speed.To construct embodiment 1 --- embodiment 4 and comparative example, and be bonded corresponding cement block and steel plate, construct
It is fixed on after 10min on revolution drum, then turned round in the seawater with the speed of about 20 nautical miles/hour.It is tested after 7 days, 28 days
Bond the pull-out strength of test block.Ocean temperature in during this is to be held in 25 DEG C, and pH is held in 8.0~8.2, and guarantees every
Replace once a week seawater.
Table 3 turns round artificial seawater Soak Test data
The beneficial effect of present embodiment is:
It is viscous in test method 1, test method 2, test method 3 using organic-silicon-modified bisphenol A type epoxy resin adhesive
Knotting strength is better than the contrast sample made of bisphenol-A epoxy, and adhesion strength decline is faint, is suitable for fresh water, seawater, ship
With the bonding repairing of equipment, the cement of wet environment contact water and steel position.
Specific embodiments of the present invention are only a part of the embodiments of the present invention, instead of all the embodiments, are not constituted
Limitation of the present invention.Based on the embodiments of the present invention, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of bisphenol type epoxy organic siliconresin, it is characterised in that: including component A, component B, component C, component D, described group
Point A is methyltriethoxysilane or diethoxy methoxy methyl base silane, the component B be dimethyl diethoxysilane or
One ethyl diethoxy silane of monomethyl, the component C be ethyl triethoxysilane or methyltriethoxysilane, described group
Dividing D is bisphenol-A type epoxy resin.
2. a kind of bisphenol type epoxy organic siliconresin as described in claim 1, it is characterised in that: the component A is methyl three
Ethoxysilane, the component B are dimethyl diethoxysilane, and the component C is ethyl triethoxysilane, the component
D is the mixture that one or both of bisphenol-A type epoxy resin E20, E44, E51, E12 are arbitrarily matched.
3. a kind of bisphenol type epoxy organic siliconresin as claimed in claim 2, it is characterised in that: including methyl triethoxy
Silane 60g, dimethyl diethoxysilane 60g and ethyl triethoxysilane 20g, bisphenol-A type epoxy resin 100g；Or
Including methyltriethoxysilane 20g, dimethyl diethoxysilane 60g and ethyl triethoxysilane 60g, bisphenol-A type
Epoxy resin 150g；Or including methyltriethoxysilane 60g, dimethyl diethoxysilane 20g and ethyl triethoxy
Silane 60g, bisphenol-A type epoxy resin 200g.
4. a kind of described in any item preparation methods of bisphenol type epoxy organic siliconresin of claim 1-3, it is characterised in that:
Steps are as follows:
1) use organoalkoxysilane for raw material, organoalkoxysilane prepares silicone oligomer by hydrolytie polycondensation, institute
Stating organoalkoxysilane includes component A, component B, component C, and the component A is methyltriethoxysilane or diethoxy first
Oxygroup methyl-monosilane, the component B are one ethyl diethoxy silane of dimethyl diethoxysilane or monomethyl, the component
C is ethyl triethoxysilane or methyltriethoxysilane；
2) secondary hydroxyl is occurred for the silicone oligomer of step 1) preparation and bisphenol A type epoxy resin to react to form bisphenol-A type ring
Oxygen organic siliconresin.
5. a kind of preparation method of bisphenol type epoxy organic siliconresin as claimed in claim 4, it is characterised in that:
Specific step is as follows for step 1): in the four-hole boiling flask for having thermometer, addition funnel, reflux condenser, agitating device
In, it is packed into dimethylbenzene 100g, is passed through under nitrogen protection, methyltriethoxysilane 60g, dimethyl diethoxysilane is added
Deionized water 5g is added dropwise after mixing evenly in 60g and ethyl triethoxysilane 20g, and the salt of 2mol/L is added dropwise after water is added dropwise
Then sour 0.5g is stirred to liquid-transparent, be warming up to 80 DEG C, is kept temperature 2h heat preservation, room temperature is cooled to after 2h, after vacuum distillation
Stopping is passed through nitrogen, obtained condensation resin is stored in closed container；
Specific step is as follows for step 2: by the bisphenol A type epoxy resin of 100g, 50g silicone oligomer and 20g cyclohexanone add
Enter and blender be housed, thermometer, in the four-hole boiling flask of reflux condenser and oil water separator, after epoxy resin all fusing plus
Entering catalyst, is stirred and heated to 150 DEG C of back flow reactions, the ethyl alcohol for reacting generation is removed by oil water separator, after reaction to 3h, drop
Temperature, filtering, packaging, are made modifying epoxy resin by organosilicon.
6. a kind of preparation method of bisphenol type epoxy organic siliconresin as claimed in claim 4, it is characterised in that:
Specific step is as follows for step 1): in the four-hole boiling flask for having thermometer, addition funnel, reflux condenser, agitating device
In, it is packed into dimethylbenzene 100g, is passed through under nitrogen protection, methyltriethoxysilane 20g, dimethyl diethoxysilane is added
Deionized water 4g is added dropwise after mixing evenly in 60g and ethyl triethoxysilane 60g, and the salt of 2mol/L is added dropwise after water is added dropwise
Then sour 0.4g is stirred to liquid-transparent, be warming up to 90 DEG C, is kept temperature 4h heat preservation, room temperature is cooled to after 4h, after vacuum distillation
Stopping is passed through nitrogen, obtained condensation resin is stored in closed container；
Specific step is as follows for step 2: by the bisphenol A type epoxy resin of 150g, 50g silicone oligomer and 30g cyclohexanone add
Enter and blender be housed, thermometer, in the four-hole boiling flask of reflux condenser and oil water separator, after epoxy resin all fusing plus
Entering catalyst, is stirred and heated to 150 DEG C of back flow reactions, the ethyl alcohol for reacting generation is removed by oil water separator, after reaction to 4h, drop
Temperature, filtering, packaging, are made modifying epoxy resin by organosilicon.
7. a kind of preparation method of bisphenol type epoxy organic siliconresin as claimed in claim 4, it is characterised in that:
Specific step is as follows for step 1): in the four-hole boiling flask for having thermometer, addition funnel, reflux condenser, agitating device
In, it is packed into dimethylbenzene 100g, is passed through under nitrogen protection, methyltriethoxysilane 60g, dimethyl diethoxysilane is added
Deionized water 3g is added dropwise after mixing evenly in 20g and ethyl triethoxysilane 60g, and the salt of 2mol/L is added dropwise after water is added dropwise
Then sour 0.3g is stirred to liquid-transparent, be warming up to 100 DEG C, is kept temperature 5h heat preservation, is cooled to room temperature after 5h, is evaporated under reduced pressure
Stop being passed through nitrogen afterwards, obtained condensation resin is stored in closed container；
Specific step is as follows for step 2: by the bisphenol A type epoxy resin of 200g, 50g silicone oligomer and 40g cyclohexanone add
Enter and blender be housed, thermometer, in the four-hole boiling flask of reflux condenser and oil water separator, after epoxy resin all fusing plus
Entering catalyst, is stirred and heated to 150 DEG C of back flow reactions, the ethyl alcohol for reacting generation is removed by oil water separator, after reaction to 5h, drop
Temperature, filtering, packaging, are made modifying epoxy resin by organosilicon.
8. a kind of bisphenol type epoxy organic silicon resin adhesive, it is characterised in that: the bisphenol type epoxy organic siliconresin gluing
It is solid that the group that agent includes is divided into bisphenol type epoxy organic siliconresin obtained, hydrophobic type resin material, resting form according to the method described above
Agent, modified amine, special dry promotor, dimethylbenzene, n-butanol, surfactant, filler, wherein the adhesive components
Are as follows: in terms of mass parts, 18-24 parts of bisphenol type epoxy organic siliconresin, 5-8 parts of hydrophobic type resin material, latent curing agent
0.1-1 parts, 1-4 parts of modified amine, dry promotor 0.7-5 parts special, 9-16 parts of dimethylbenzene, 9-16 parts of n-butanol, surface-active
0.2-0.8 parts of agent, 40-57 parts of filler.
9. a kind of bisphenol type epoxy organic silicon resin adhesive as claimed in claim 8, it is characterised in that: the adhesive
Component are as follows: in terms of mass parts, 20 parts of bisphenol type epoxy organic siliconresin, 7 parts of hydrophobic type resin material, latent curing agent 1
Part, 3 parts of modified amine, special 0.8 part of dry promotor, 11 parts of dimethylbenzene, 11 parts of n-butanol, 0.6 part of surfactant, filler
45.6 parts.
10. a kind of preparation method of bisphenol type epoxy organic silicon resin adhesive, feature described in claim 8 or 9 exist
In: steps are as follows:
(1) raw material is weighed according to the ratio, and part dimethylbenzene and part n-butanol are mixed and made into solvent, part is first added into solvent
Organic-silicon-modified bisphenol A type epoxy resin sequentially adds surfactant, filler, hydrophobic type resinous wood after mixing evenly
Material, after being uniformly dispersed, is placed in grinder and grinds, until fineness of grind is less than or equal to 20 microns, ground mill base is set
In clean stirred tank, remaining organic-silicon-modified bisphenol A type epoxy resin, remaining diformazan are sequentially added under agitation
Benzene and n-butanol, after mixing evenly, fineness filter and package discharging at 20 microns or less；
(2) modified amine, latent curing agent, special dry promotor are weighed by formula ratio, stirs evenly, filters and packages discharging；
(3) then stir with paint according to the ratio that quality proportioning is 2:1 by the product of step (1) and by the product of step (2)
Agitating is even up to bisphenol type epoxy organic silicon resin adhesive.
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| CN112411372A (en) * | 2020-11-25 | 2021-02-26 | 上海浦兴路桥建设工程有限公司 | Thin-layer epoxy polymer concrete suitable for steel box girder bridge floor and preparation method thereof |
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| CN115926620A (en) * | 2022-12-08 | 2023-04-07 | 江苏三木化工股份有限公司 | High-performance blue epoxy polysiloxane coating and preparation method thereof |
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| CN112411372A (en) * | 2020-11-25 | 2021-02-26 | 上海浦兴路桥建设工程有限公司 | Thin-layer epoxy polymer concrete suitable for steel box girder bridge floor and preparation method thereof |
| CN115926620A (en) * | 2022-12-08 | 2023-04-07 | 江苏三木化工股份有限公司 | High-performance blue epoxy polysiloxane coating and preparation method thereof |
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