CN110305609A - A kind of bi-component flexible compound epoxy resin adhesive - Google Patents
A kind of bi-component flexible compound epoxy resin adhesive Download PDFInfo
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- CN110305609A CN110305609A CN201910505810.5A CN201910505810A CN110305609A CN 110305609 A CN110305609 A CN 110305609A CN 201910505810 A CN201910505810 A CN 201910505810A CN 110305609 A CN110305609 A CN 110305609A
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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
- C09J11/08—Macromolecular additives
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of bi-component flexible compound epoxy resin adhesives, belong to technical field of polymer materials.According to parts by weight, it successively weighs: 60~100 parts of blending epoxies, 8~15 parts of catalyst, 12~18 parts of epoxidized soybean oils, 2~5 parts of curing accelerators, 2~8 parts of silane coupling agents, 10~15 portions of reactive diluents and 20~30 parts of additives, blending epoxy and catalyst are mixed in blender, and sequentially add epoxidized soybean oil into blender, curing accelerator, silane coupling agent, reactive diluent and additive after being stirred 60~80min, obtain component A；The B component is mixed curing agent, and component A and B component are separately encapsulated to get bi-component flexible compound epoxy resin adhesive.Bi-component flexible compound epoxy resin gluing provided by the invention has excellent adhesion strength, and the toughness of product is preferable, has excellent market prospects.
Description
Technical field
The invention discloses a kind of bi-component flexible compound epoxy resin adhesives, belong to technical field of polymer materials.
Background technique
Epoxyn is that one kind is formulated by epoxy resin base, curing agent, diluent, promotor and filler
Engineering adhesive.Since its adhesive property is good, functional good, less expensive, technique for sticking simplicity, so recent decades
To be widely used in household electrical appliances, automobile, water conservancy traffic, electronic apparatus and aerospace industry field.With new and high technology and
The continuous development of nanotechnology in recent years deepens continuously to the modification of epoxy resin, interpenetrating networks, chemical copolymerization and nanoparticle
The methods of sub- toughening be widely applied, by epoxy preparation at various high-performance adhesive kinds it is also more and more.
But with the successive proposition of the various gluing theories of 20 middle of century and adhesive chemistry, adhesive rheology
With the deep progress of the basic research works such as gluing failure mechanism, there are Adhensive performance, kind and application and advance by leaps and bounds
Development.Epoxy resin and its curing system also unique with its, excellent performance and neo-epoxy resin, Novel curing agent and add
Add continuing to bring out for agent, become have excellent performance, kind is numerous, the extensive a kind of important adhesive of adaptability.
Epoxy resin epoxy resin be in molecule containing two or more epoxy groups and relative molecular mass is lower
High-molecular compound one, the classify kind of epoxy resin, the trade mark it is very much, but bis-phenol A glycidyl ether epoxy resin is commonly referred to as
It is most important one kind for bisphenol A epoxide resin.It accounts for the 90% of epoxy resin total output.Bisphenol A type epoxy resin is also known as general
Type epoxy resin and standard type epoxy resin are named as E type epoxy resin, by bis-phenol (BPA or DPP) and epoxychloropropane
(ECH) under sodium hydroxide polycondensation and obtain.
It is different according to the method for raw material proportioning, reaction condition and use, the low average molecular matter of different polymerization degree can be made
The thick liquid of amount and high relative molecular mass, high softening-point solid.Average molecular mass 300-7000.Appearance is intimate
Colourless or pale yellow transparent thick liquid or sheet brittle solid.Epoxy resin itself is thermoplastic novolac polymer, when being heated
Liquid resin viscosity, hard resin are softened or melted.Be dissolved in acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, benzene, toluene,
The organic solvents such as dimethylbenzene, dehydrated alcohol, ethylene glycol.
Traditional normal-temperature curing epoxy Resin adhesive usually has very high crosslink density and causes its quality brittle, tough
Property it is insufficient, poor flexibility is mainly shown as that tensile strength is very big in mechanical property, and elongation at break is small, and there are no fatigue durabilitys
It can say.Therefore, most of normal-temperature curing epoxy adhesives are mainly used for structure in road, bridge and building engineering field
Glue, casting glue, anchoring adhesive and anticorrosive paint etc..Road and bridge will be subjected to the work of traffic loading repeatedly in actual use
With, while temperature change also will appear material temperature and contract inconsistent and generate temperature stress, this requires road antiskid coatings and bridge
Water-proof bond material mat formation with flexibility and fatigue performance in face, it is clear that conventional epoxies adhesive is hard and crisp to be difficult to reach
Above-mentioned requirements, the effective ways for solving this problem are to realize that epoxy resin is flexibilized by modified.Epoxy resin it is flexibilized,
Its basic ideas is exactly to reduce the elasticity modulus of solidified resin under the premise of significantly not sacrificing adhesion strength or make its glass
Change transition temperature to low temperature shift, it is ensured that it is with low temperature flexibility.In addition, bridge waterproof bonding, road antiskid coating and building
Object waterproof construction is typically all outdoor room temperature even low-temperature construction, and this requires epoxy resin adhesives can at normal temperature quickly
Gel solidification, however room temperature rapid curing is often contradictory with epoxy flexibility after solidification, two are all difficult to get both.Currently, epoxy
The elastic adhesive of adhesive, which receives, to be paid attention to extensively and studies, and main target is using a kind of high bond strength and the high-elastic shape of tool
The technology that the adhesive of change is bonded guarantees that its stress distribution in road, bridge and building engineering field application process is equal
It is even, stress will not be generated and concentrate and destroy.
Therefore, research and development has high bond strength, and the preferable epoxy resin adhesive of toughness has preferable city
Field prospect.
Summary of the invention
The present invention solves the technical problem of: for current epoxy resin adhesive toughness, there are lances with adhesion strength
Shield the problem of can not improving together, provides a kind of bi-component flexible compound epoxy resin adhesive.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of bi-component flexible compound epoxy resin adhesive, is made of component A and B component, and the component A is by following heavy
The raw material for measuring number forms: 60~100 parts of blending epoxies, 8~15 parts of catalyst, 12~18 parts of epoxidized soybean oils, and 2~5
Part curing accelerator, 2~8 parts of silane coupling agents, 10~15 portions of reactive diluents and 20~30 parts of additives, the B component are
Mixed curing agent；
The additive the preparation method comprises the following steps:
(1) silica is mixed with hydrochloric acid 1:10~1:15 in mass ratio, is stirred to react, filtered, washed, dry, calcining obtains
Activated silica；
(2) activated silica is mixed with silane resin acceptor kh-550 1:2~1:3 in mass ratio, and activation titanium dioxide is added
The dehydrated alcohol of 10~12 times of siliceous amount after being stirred to react, stands, filters, dry, obtains amination silica；
(3) amination silica is mixed with methanol 1:15~1:18 in mass ratio, and amination silica quality 2 is added
~3 times of acrylic acid, under nitrogen atmosphere, after being stirred to react, filtering obtains pre- improved silica blank, by pre- modified dioxy
SiClx purification by liquid extraction, it is dry, obtain pre- improved silica；
(4) pre- improved silica is mixed with ethylenediamine 1:1~1:2 in mass ratio, and pre- improved silica quality 8 is added
~10 times of methanol, after being stirred to react under nitrogen atmosphere, filtering obtains improved silica blank；
(5) dry by improved silica blank purification by liquid extraction, improved silica is obtained to get additive.
The blending epoxy is to mix epoxy resin E-44 with epoxy resin E-51 1:1~2:1 in mass ratio, is obtained
Blending epoxy.
The catalyst is any one in magnesium chloride or zinc chloride.
The reactive diluent is any one in polypropylene glycol diglycidyl ether or 1,4- butanediol diglycidyl ether
Kind.
The curing accelerator is to mix curing accelerator DMP-30 and nonyl phenol NP 2:1 in mass ratio, must solidify rush
Into agent.
The silane coupling agent is silane resin acceptor kh-550, in silane coupling agent KH-560 or Silane coupling reagent KH-570
Any one.
The mixed curing agent mixes ethylenediamine with m-phenylene diamine (MPD) 1:1~2:1 in mass ratio, obtains mixed curing agent.
The pretreatment graphene oxide of blending epoxy quality 3~5% can also be added in the blending epoxy；
The preprocessing process of the pretreatment graphene oxide are as follows: by graphene oxide and isocyanates be in mass ratio that 1:3~1:5 is mixed
After conjunction, heating stirring reaction, using filter, washing and vacuum drying obtain pretreatment graphene oxide.
The application method of the bi-component flexible compound epoxy resin adhesive are as follows: be in mass ratio by component A and B component
After 5:1~10:1 mixing, it is stirred 3~5min, that is, can be used.
The beneficial effects of the present invention are:
(1) additive and epoxidized soybean oil are added when preparing bi-component flexible compound epoxy resin adhesive by the present invention, utilize
The two cooperates to solve technical problem, during specifically playing a role, firstly, containing dioxy in the additive being added
SiClx, and silica surface is successively grafted acrylate and ethylenediamine segment in additive preparation process, is being added
After in product, on the one hand, since silica itself can be used as hard core, the effect of enhanced additive is played, so as to
Improve the adhesion strength of product, on the other hand, the acrylate and ethylenediamine segment of silica surface grafting can be with rings
Oxygen resin macromolecule chain generates winding, makes shape between the macromolecular chain of epoxy resin and the macromolecular chain of silica surface grafting
Ratcheting at machinery, a degree of contraction and relative displacement can occur for the ratcheting structure formed both in loading process, thus
The toughness of product is improved, Cracking Failure is effectively prevented；Secondly, the epoxidized soybean oil being added can be in catalyst and mixing cured
It is crosslinked under the action of agent with the compound containing primary amino group, since silica surface is grafted upper acrylate and second two
After amine segment, silica surface contains primary amine group, and therefore, in product solidification process, additive can be with epoxidized soybean oil
Reaction is crosslinked, to improve the crosslinking degree of interiors of products, and forms soft segment in the product, and then makes the viscous of product
Knotting strength improves, toughness enhancing；And the group as contained by the segment of silica surface grafting is handed over epoxidized soybean oil
Connection, to improve the interface binding power and interface compatibility between inorganic silica and organic resin matrix, makes
Product mechanical property is further promoted；
(2) technical solution of the present invention in system by introducing isocyanate-modified graphene oxide, isocyanate-modified
In the process, isocyanates can be active with institute's band on the carboxyl for the hydroxyl and edge for being conjugated area in graphene oxide molecular structure
Hydrogen reaction, so that being conjugated area and edge in graphene oxide molecular structure introduces isocyanate molecule chain, isocyanates point
The introducing of subchain can effectively promote graphene oxide interlamellar spacing, and product adhesive component is made to be efficiently entering graphene oxide interlayer,
Making graphene oxide that the distribution of monolithic layer structural separation be presented in adhesive system can be during adhesive curing molding
Continuous lamellar structure is formed in adhesive system, further promotes the toughness of product.
Specific embodiment
It is in mass ratio heating stirring reaction after 1:3~1:5 is mixed by graphene oxide and isocyanates, using filter,
Washing and vacuum drying, obtain pretreatment graphene oxide；By silica and mass fraction be 10~12% hydrochloric acid in mass ratio
1:10~1:15 mixing is 110~120 DEG C in temperature, under conditions of revolving speed is 300~400r/min, is stirred to react 3~4h
Afterwards, it filters, obtains activated silica blank, activated silica blank is washed with deionized after being neutral to cleaning solution,
And under conditions of in temperature being 80~100 DEG C after dry 1~2h, then at temperature be 200~300 DEG C under conditions of calcine 1~2h
Afterwards, activated silica is obtained, activated silica and silane resin acceptor kh-550 1:2~1:3 in mass ratio are mixed in flask
In, and 10~12 times of activated silica quality of dehydrated alcohol is added into flask, it is 75~85 DEG C in temperature, revolving speed is
2~3h is stirred to react under conditions of 300~400r/min, after standing 2~3h under room temperature, filtering obtains amination two
Silicon blank is aoxidized, under conditions of being 70~80 DEG C in temperature by amination silica blank after dry 2~3h, obtains amination two
Amination silica and methanol 1:15~1:18 in mass ratio are mixed in three-necked flask by silica, and to three-necked flask
The middle acrylic acid that 2~3 times of amination silica quality is added, is passed through nitrogen into three-necked flask with the rate of 20~30mL/min
Gas is 30~45 DEG C in temperature, and under conditions of revolving speed is 200~350r/min, after being stirred to react 3~4 days, filtering obtains pre- change
Property silica blank, by pre- improved silica in Soxhlet extractor first with methanol in temperature be 80~85 DEG C under conditions of
Extract 5~8h after, then with tetrahydrofuran in temperature be 80~90 DEG C under conditions of extraction 8~10h, pre- modified titanium dioxide must be purified
Silicon blank will purify after being dried in vacuo 1~2h under conditions of pre- improved silica blank is 110 DEG C in temperature, and obtain pre- modification
Pre- improved silica and ethylenediamine 1:1~1:2 in mass ratio are mixed in four-hole boiling flask by silica, and are burnt to four mouthfuls
The methanol of 8~10 times of pre- improved silica quality is added in bottle, is passed through into four-hole boiling flask with the rate of 20~30mL/min
Nitrogen is 50~60 DEG C in temperature, and under conditions of revolving speed is 300~350r/min, after being stirred to react 4~5h, filtering obtains modification
Silica blank, by improved silica blank first with methanol under conditions of temperature is 80~85 DEG C in Soxhlet extractor
Extract 5~8h after, then with tetrahydrofuran in temperature be 80~90 DEG C under conditions of extraction 8~10h, obtain purified modified silica
Blank must be modified two after being dried in vacuo 1~2h under conditions of being 100~120 DEG C in temperature by purified modified silica blank
Silica is to get additive, according to parts by weight, successively weighs: 60~100 parts of blending epoxies, 8~15 parts of catalyst,
12~18 parts of epoxidized soybean oils, 2~5 parts of curing accelerators, 2~8 parts of silane coupling agents, 10~15 portions of reactive diluents and 20~
The pretreatment graphene oxide of 30 parts of additives and blending epoxy quality 3~5%, by blending epoxy and catalyst
It is mixed in blender, and sequentially adds epoxidized soybean oil into blender, curing accelerator, silane coupling agent, activity dilution
Agent, additive and pretreatment graphene oxide are 30~40 DEG C in temperature, under conditions of revolving speed is 200~350r/min, stir
After mixing 60~80min, component A is obtained；The B component is mixed curing agent；Component A and B component are separately encapsulated to get double groups
Divide flexible compound epoxy resin adhesive.The blending epoxy is that epoxy resin E-44 and epoxy resin E-51 are pressed quality
It is mixed than 1:1~2:1, obtains blending epoxy.The catalyst is any one in magnesium chloride or zinc chloride.The activity is dilute
Releasing agent is any one in polypropylene glycol diglycidyl ether or 1,4- butanediol diglycidyl ether.The curing accelerator is
Curing accelerator DMP-30 and nonyl phenol NP 2:1 in mass ratio is mixed, curing accelerator is obtained.The silane coupling agent is silane
Any one in coupling agent KH-550, silane coupling agent KH-560 or Silane coupling reagent KH-570.The mixed curing agent is by second
Diamines is mixed with m-phenylene diamine (MPD) 1:1~2:1 in mass ratio, obtains mixed curing agent.
Example 1
In mass ratio it is heating stirring reaction after 1:5 is mixed by graphene oxide and isocyanates, using filter, washs and true
Sky is dry, obtains pretreatment graphene oxide；Silica is mixed with the hydrochloric acid 1:15 in mass ratio that mass fraction is 12%, in
Temperature is 120 DEG C, and under conditions of revolving speed is 400r/min, after being stirred to react 4h, filtering obtains activated silica blank, will live
Change after silica blank is washed with deionized and is neutral to cleaning solution, and under conditions of being 100 DEG C in temperature after dry 2h,
Then at temperature be 300 DEG C under conditions of calcine 2h after, activated silica is obtained, by activated silica and silane coupling agent KH-
550 1:3 in mass ratio are mixed in flask, and 12 times of activated silica quality of dehydrated alcohol, Yu Wen are added into flask
Degree is 85 DEG C, and revolving speed is stirred to react 3h under conditions of being 400r/min, and after standing 3h under room temperature, filtering obtains amino
Change silica blank, under conditions of being 80 DEG C in temperature by amination silica blank after dry 3h, obtains amination dioxy
Amination silica and methanol 1:18 in mass ratio are mixed in three-necked flask, and ammonia are added into three-necked flask by SiClx
The acrylic acid of 3 times of base silica quality, is passed through nitrogen into three-necked flask with the rate of 30mL/min, in temperature be 45
DEG C, under conditions of revolving speed is 350r/min, after being stirred to react 4 days, filtering obtains pre- improved silica blank, by pre- modification two
Silica in Soxhlet extractor first with methanol be 85 DEG C in temperature under conditions of extract 8h after, then with tetrahydrofuran be in temperature
10h is extracted under conditions of 90 DEG C, pre- improved silica blank must be purified, will purify pre- improved silica blank in temperature is
After being dried in vacuo 2h under conditions of 110 DEG C, pre- improved silica is obtained, by pre- improved silica and ethylenediamine in mass ratio 1:
2 are mixed in four-hole boiling flask, and the methanol of 10 times of pre- improved silica quality is added into four-hole boiling flask, into four-hole boiling flask
Be passed through nitrogen with the rate of 30mL/min, in temperature be 60 DEG C, revolving speed be 350r/min under conditions of, after being stirred to react 5h, mistake
Filter, obtains improved silica blank, by improved silica blank in Soxhlet extractor first with methanol in temperature be 85 DEG C
Under the conditions of extract 8h after, then with tetrahydrofuran extract 10h under the conditions of at a temperature of 90 °C, obtain purified modified silica base
Material obtains improved silica, i.e., after being dried in vacuo 2h under conditions of being 120 DEG C in temperature by purified modified silica blank
Additive is obtained successively to weigh according to parts by weight: 100 parts of blending epoxies, 15 parts of catalyst, 18 parts of epoxidized soybean oils, 5
Part curing accelerator, 8 parts of silane coupling agents, 15 portions of reactive diluents, 30 parts of additives and blending epoxy quality 5%
Graphene oxide is pre-processed, blending epoxy and catalyst are mixed in blender, and sequentially add ring into blender
Oxygen soybean oil, curing accelerator, silane coupling agent, reactive diluent, additive and pretreatment graphene oxide, in temperature be 40
DEG C, under conditions of revolving speed is 350r/min, after being stirred 80min, obtain component A；The B component is mixed curing agent；By A group
Divide and B component separately encapsulates to get bi-component flexible compound epoxy resin adhesive.The blending epoxy is by asphalt mixtures modified by epoxy resin
Rouge E-44 is mixed with epoxy resin E-51 2:1 in mass ratio, obtains blending epoxy.The catalyst is zinc chloride.The work
Property diluent be polypropylene glycol diglycidyl ether.The curing accelerator is to press curing accelerator DMP-30 and nonyl phenol NP
Mass ratio 2:1 mixing, obtains curing accelerator.The silane coupling agent is Silane coupling reagent KH-570.The mixed curing agent will
Ethylenediamine is mixed with m-phenylene diamine (MPD) 1:1 in mass ratio, obtains mixed curing agent.
Example 2
The hydrochloric acid 1:15 in mass ratio that silica and mass fraction are 12% mix, in temperature be 120 DEG C, revolving speed 400r/
Under conditions of min, after being stirred to react 4h, filtering obtains activated silica blank, by activated silica blank deionized water
After washing is neutral to cleaning solution, and under conditions of being 100 DEG C in temperature after dry 2h, under conditions of being 300 DEG C then at temperature
After calcining 2h, activated silica is obtained, activated silica and silane resin acceptor kh-550 1:3 in mass ratio are mixed in flask
In, and 12 times of activated silica quality of dehydrated alcohol is added into flask, it is 85 DEG C in temperature, revolving speed is 400r/min's
Under the conditions of be stirred to react 3h, then under room temperature stand 3h after, filtering, amination silica blank is obtained, by amination two
Under conditions of oxidation silicon blank is 80 DEG C in temperature after dry 3h, amination silica is obtained to get additive, in parts by weight
Meter, successively weighs: 100 parts of blending epoxies, 15 parts of catalyst, 18 parts of epoxidized soybean oils, 5 parts of curing accelerators, 8 parts of silane
Blending epoxy and catalyst are mixed in blender by coupling agent, 15 portions of reactive diluents and 30 parts of additives, and to stirring
Mix and sequentially add epoxidized soybean oil in machine, curing accelerator, silane coupling agent, reactive diluent and additive, in temperature be 40
DEG C, under conditions of revolving speed is 350r/min, after being stirred 80min, obtain component A；According to parts by weight, it successively weighs: the B
Component is mixed curing agent, and component A and B component are separately encapsulated to get bi-component flexible compound epoxy resin adhesive.It is described
Blending epoxy is to mix epoxy resin E-44 with epoxy resin E-51 2:1 in mass ratio, obtains blending epoxy.It is described
Catalyst is zinc chloride.The reactive diluent is polypropylene glycol diglycidyl ether.The curing accelerator is that will solidify rush
It is mixed into agent DMP-30 and nonyl phenol NP 2:1 in mass ratio, obtains curing accelerator.The silane coupling agent is silane coupling agent
KH-570.The mixed curing agent mixes ethylenediamine with m-phenylene diamine (MPD) 1:1 in mass ratio, obtains mixed curing agent.
Example 3
The hydrochloric acid 1:15 in mass ratio that silica and mass fraction are 12% mix, in temperature be 120 DEG C, revolving speed 400r/
Under conditions of min, after being stirred to react 4h, filtering obtains activated silica blank, by activated silica blank deionized water
After washing is neutral to cleaning solution, and under conditions of being 100 DEG C in temperature after dry 2h, under conditions of being 300 DEG C then at temperature
After calcining 2h, activated silica is obtained, activated silica and silane resin acceptor kh-550 1:3 in mass ratio are mixed in flask
In, and 12 times of activated silica quality of dehydrated alcohol is added into flask, it is 85 DEG C in temperature, revolving speed is 400r/min's
Under the conditions of be stirred to react 3h, then under room temperature stand 3h after, filtering, amination silica blank is obtained, by amination two
Under conditions of oxidation silicon blank is 80 DEG C in temperature after dry 3h, amination silica is obtained, by amination silica and first
Alcohol 1:18 in mass ratio is mixed in three-necked flask, and the propylene of 3 times of amination silica quality is added into three-necked flask
Acid is passed through nitrogen into three-necked flask with the rate of 30mL/min, in temperature be 45 DEG C, revolving speed be 350r/min under conditions of,
After being stirred to react 4 days, filtering obtains pre- improved silica blank, pre- improved silica is first used first in Soxhlet extractor
After alcohol extracts 8h under conditions of being 85 DEG C in temperature, then with tetrahydrofuran 10h is extracted under the conditions of at a temperature of 90 °C, must purify
Pre- improved silica blank will purify after being dried in vacuo 2h under conditions of pre- improved silica blank is 110 DEG C in temperature,
Pre- improved silica is obtained to get additive, according to parts by weight, is successively weighed: 100 parts of blending epoxies, 15 parts of catalysis
Agent, 18 parts of epoxidized soybean oils, 5 parts of curing accelerators, 8 parts of silane coupling agents, 15 portions of reactive diluents and 30 parts of additives, will mix
It closes epoxy resin and catalyst is mixed in blender, and sequentially add epoxidized soybean oil into blender, curing accelerator, silicon
Alkane coupling agent, reactive diluent and additive are 40 DEG C in temperature, under conditions of revolving speed is 350r/min, are stirred 80min
Afterwards, component A is obtained；The B component is mixed curing agent, and component A and B component are separately encapsulated to get bi-component flexible compound ring
Epoxy resin adhesive.The blending epoxy is to mix epoxy resin E-44 with epoxy resin E-51 2:1 in mass ratio, is obtained
Blending epoxy.The catalyst is zinc chloride.The reactive diluent is polypropylene glycol diglycidyl ether.The solidification
Promotor is to mix curing accelerator DMP-30 and nonyl phenol NP 2:1 in mass ratio, obtains curing accelerator.It is described silane coupled
Agent is Silane coupling reagent KH-570.The mixed curing agent mixes ethylenediamine with m-phenylene diamine (MPD) 1:1 in mass ratio, must mix solid
Agent.
Comparative example: the epoxy resin adhesive of Shenzhen Jiao Ye Co., Ltd production.
1 to 3 gained bi-component flexible compound epoxy resin adhesive of example and comparative example product are subjected to performance detection, tool
Body detecting method is as follows:
1. tensile strength: being tested for the property according to 7124 standard of GB/T, specific testing result is as shown in table 1；
2. elongation at break: specific testing result is as shown in table 1；
1 tensile strength of table and elongation at break particular exam result
| Detection content | Example 1 | Example 2 | Example 3 | Comparative example |
| Tensile strength/MPa | 66.8 | 30.5 | 45.6 | 44.7 |
| Elongation at break/% | 120.4 | 88.6 | 98.7 | 94.6 |
By 1 testing result of table it is found that bi-component flexible compound epoxy resin gluing provided by the invention has excellent bonding strong
Degree, and the toughness of product is preferable, has excellent market prospects.
Claims (9)
1. a kind of bi-component flexible compound epoxy resin adhesive, is made of component A and B component, it is characterised in that: the A
Component is made of the raw material of following parts by weight: 60~100 parts of blending epoxies, 8~15 parts of catalyst, 12~18 parts of rings
Oxygen soybean oil, 2~5 parts of curing accelerators, 2~8 parts of silane coupling agents, 10~15 portions of reactive diluents and 20~30 parts of additions
Agent；
The B component is mixed curing agent；
The additive the preparation method comprises the following steps:
(1) silica is mixed with hydrochloric acid 1:10~1:15 in mass ratio, is stirred to react, filtered, washed, dry, calcining obtains
Activated silica；
(2) activated silica is mixed with silane resin acceptor kh-550 1:2~1:3 in mass ratio, and activation titanium dioxide is added
The dehydrated alcohol of 10~12 times of siliceous amount after being stirred to react, stands, filters, dry, obtains amination silica；
(3) amination silica is mixed with methanol 1:15~1:18 in mass ratio, and amination silica quality 2 is added
~3 times of acrylic acid, under nitrogen atmosphere, after being stirred to react, filtering obtains pre- improved silica blank, by pre- modified dioxy
SiClx purification by liquid extraction, it is dry, obtain pre- improved silica；
(4) pre- improved silica is mixed with ethylenediamine 1:1~1:2 in mass ratio, and pre- improved silica quality 8 is added
~10 times of methanol, after being stirred to react under nitrogen atmosphere, filtering obtains improved silica blank；
(5) dry by improved silica blank purification by liquid extraction, improved silica is obtained to get additive.
2. a kind of bi-component flexible compound epoxy resin adhesive according to claim 1, it is characterised in that: the mixing
Epoxy resin is to mix epoxy resin E-44 with epoxy resin E-51 1:1~2:1 in mass ratio, obtains blending epoxy.
3. a kind of bi-component flexible compound epoxy resin adhesive according to claim 1, it is characterised in that: the catalysis
Agent is any one in magnesium chloride or zinc chloride.
4. a kind of bi-component flexible compound epoxy resin adhesive according to claim 1, it is characterised in that: the activity
Diluent is any one in polypropylene glycol diglycidyl ether or 1,4- butanediol diglycidyl ether.
5. a kind of bi-component flexible compound epoxy resin adhesive according to claim 1, it is characterised in that: the solidification
Promotor is to mix curing accelerator DMP-30 and nonyl phenol NP 2:1 in mass ratio, obtains curing accelerator.
6. a kind of bi-component flexible compound epoxy resin adhesive according to claim 1, it is characterised in that: the silane
Coupling agent is silane resin acceptor kh-550, any one in silane coupling agent KH-560 or Silane coupling reagent KH-570.
7. a kind of bi-component flexible compound epoxy resin adhesive according to claim 1, it is characterised in that: the mixing
Curing agent mixes ethylenediamine with m-phenylene diamine (MPD) 1:1~2:1 in mass ratio, obtains mixed curing agent.
8. a kind of bi-component flexible compound epoxy resin adhesive according to claim 1, it is characterised in that: the mixing
The pretreatment graphene oxide of blending epoxy quality 3~5% can also be added in epoxy resin；The pretreatment aoxidizes stone
The preprocessing process of black alkene are as follows: by graphene oxide and isocyanates be in mass ratio 1:3~1:5 mix after, heating stirring is anti-
It answers, using filter, washing and vacuum drying obtain pretreatment graphene oxide.
9. a kind of bi-component flexible compound epoxy resin adhesive according to claim 1, it is characterised in that: described double groups
The application method of point flexible compound epoxy resin adhesive are as follows: be in mass ratio after 5:1~10:1 is mixed by component A and B component,
It is stirred 3~5min, that is, can be used.
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| CN111777981A (en) * | 2020-07-24 | 2020-10-16 | 安徽大松树脂有限公司 | Epoxy resin two-component polyurethane adhesive and preparation method thereof |
| CN112980372A (en) * | 2019-12-16 | 2021-06-18 | 深圳市优宝新材料科技有限公司 | Adhesive and preparation method thereof |
| CN113354795A (en) * | 2021-06-30 | 2021-09-07 | 江苏扬农化工集团有限公司 | Hyperbranched epoxy resin and preparation method and application thereof |
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Cited By (5)
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| CN112980372A (en) * | 2019-12-16 | 2021-06-18 | 深圳市优宝新材料科技有限公司 | Adhesive and preparation method thereof |
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| CN113354795A (en) * | 2021-06-30 | 2021-09-07 | 江苏扬农化工集团有限公司 | Hyperbranched epoxy resin and preparation method and application thereof |
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