CN109749682A - A kind of flame retardant epoxy adhesive peculiar to vessel - Google Patents
A kind of flame retardant epoxy adhesive peculiar to vessel Download PDFInfo
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- CN109749682A CN109749682A CN201811595160.XA CN201811595160A CN109749682A CN 109749682 A CN109749682 A CN 109749682A CN 201811595160 A CN201811595160 A CN 201811595160A CN 109749682 A CN109749682 A CN 109749682A
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Abstract
The invention discloses a kind of flame retardant epoxy adhesive peculiar to vessel, including component A and B component；The composition of the component A is calculated by weight as: phosphorous epoxy resin 40-60；Fire-proof function component 20-40；Inorganic filler 5-10；Thixotropic agent 5-10；Defoaming agent 0.1-3；The composition of the component B is calculated by weight as: phosphorous epoxy hardener 60-80；Thixotropic agent 1-5；Defoaming agent 0.1-2.Instant component B uses phosphorous epoxy hardener, can solve the disadvantage of high temperature resistant epoxy adhesive curing process harshness in room temperature curing, not only increases adhesive temperature tolerance and mechanical property under the conditions of flame retardant property and room temperature curing and does not decline；Medium-resistance is excellent simultaneously.By being used in compounding for inorganic filler and thixotropic agent, enable adhesive that there is fabulous sag resistance, improves convenience for construction, while the inorganic fillers such as expanded graphite alkene, zinc borate and antimony oxide have good smoke-suppressing.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of flame retardant epoxy adhesive peculiar to vessel.
Background technique
Epoxy resin refers to the general name of the quasi polymer containing more than two epoxy groups in molecule.It is by epoxy chloropropionate
The polycondensation product of alkane and bisphenol-A or polyalcohol.Since the chemical property of epoxy group is active, a variety of chemical combination containing active hydrogen can be used
Object makes its open loop, and solidification crosslinking becomes reticular structure.Epoxy adhesive is prepared by matrix of epoxy resin, has bonding
Property the strong, series of advantages such as cure shrinkage is small, corrosion resistance and good, processing performance are good.Because epoxy adhesive is a series of
Advantage is widely used for the every field such as aerospace, high-speed rail train, military affairs.It is right with scientific and technological level progress and raising
The comprehensive performance requirement of epoxy resin is higher and higher, but since its own elongation is low, big, easy firing of brittleness etc. lacks after solidification
It falls into, limits its application.
P elements are introduced to the curing agent of epoxy resin, and it is largely effective for assigning cured product simultaneously to have anti-flammability
, such as Chinese patent CN1681865, United States Patent (USP) 4973631,6403220 and Japan Patent JP61134395, they are all used
With can and epoxy resin reaction the substituted oxidation phosphorus species such as group such as amido, sulfydryl, phenolic hydroxyl group, can with ring
Oxygen resin room temperature fast-curing, but the defect bad there are still resistance to medium, influence use scope and performance.
Expansion type flame retardant is the halogen-free environment-friendly type flame-proof that one kind that new development in recent years is got up has applications well prospect
Agent.The advantages such as it is high with flame retarding efficiency, smoke amount is small, low toxic, additive amount are small have become fire proofing since entering the new century
One of research field the most popular.The fire-retardant mechanism of expansion type flame retardant is, in thermal histories, by being formed on the surface of the material
Porous foam coke layer plays fire retardation in condensed phase.Expansion type flame retardant is a flame-retardant system, generally by acid source, carbon source
It is formed with gas source three parts.Acid source mainly has the compound for promoting carbon containing polyol compound dehydration, common acid
Source is inorganic acids or can produce the compound of inorganic acid after being heated within the scope of 100~250 DEG C, common are phosphoric acid, phosphoric acid
The series compounds such as ammonium salt, phosphate.Carbon source is the compound that there is dehydration carbonization to form the effect of foam charring layer, mostly high-carbon
The polyol compound of content or its copolymer.Carbon content and activity hydroxy content in carbon source are to the foam layer of charcoal of formation
Quality is closely related, should react at lower temperature with acid source before itself or matrix are decomposed.Common can be used as carbon source
Substance have starch, pentaerythrite and its polymer, organic resin in molecule with multi-hydroxy etc..Gas source is that have suitable
The compound of a large amount of non-flammable gases foaming and intumescing effects is decomposed and can released at a temperature of.Common can be used as gas source
The substance of foaming agent has melamine, dicyandiamide, the amides such as melamine cyanurate, ammonium polyphosphate or ammonium class compound.It is common
Expansion type flame retardant be by containing P, C, N are the halogen-free flame retardants that main core element is constituted.P elements are acid source, nitrogen
For gas source.Carbon source is polyol or the carbohydrate containing higher carbon content.Ammonium polyphosphate-melamine-season
Penta tetrol (APP-MEL-PER) is traditional Intumescent Retardant System, but as adhesive is using more and more extensive, is developed more
More Intumescent Retardant Systems.
Summary of the invention
It is an object of that present invention to provide a kind of phosphorous epoxy hardeners, and which overcome existing phosphorous epoxy hardener, there are resistance to
Flame retardant epoxy adhesive peculiar to vessel is prepared in the case where not influencing use scope and behavior pattern for the bad defect of medium, in conjunction with
Requirement peculiar to vessel is a kind of high-performance, nontoxic, fire-retardant, with excellent workability normal-temperature curing epoxy adhesive.
In order to achieve the above objectives, as follows using technical solution:
A kind of flame retardant epoxy adhesive peculiar to vessel, including component A and B component；
The composition of the component A is calculated by weight as:
The composition of the component B is calculated by weight as:
Phosphorous epoxy hardener 60-80
Thixotropic agent 1-5
Defoaming agent 0.1-2.
According to the above scheme, the phosphorous epoxy resin is phosphorous DOPO epoxy resin, is that Jinan holy well group share is limited
The SQEP-803EK75 of company.
According to the above scheme, the phosphorous epoxy hardener chemical formula are as follows:
According to the above scheme, the phosphorous epoxy hardener the preparation method is as follows:
Glycidol is dissolved in tetrahydrofuran (THF), triethylamine is added and is stirred to react and controls temperature at 70 DEG C or so；Add
Enter Cu2Cl2The reaction of phenyl dichloro phosphate is added dropwise afterwards；It is filtered after standing, collects filtrate, extracted with ethyl acetate (EA), collect extraction
Take liquid；It is concentrated after drying, purifying obtains target product.
According to the above scheme, the fire-proof function component is by mass percentage are as follows:
Ammonium polyphosphate (APP) 50wt%；Carbon forming agent pentaerythrite (PER) 25-30wt%, foaming agent melamine
(MEL) 20-25wt%.
According to the above scheme, the inorganic filler is one or more of expanded graphite alkene, zinc borate and antimony oxide.
According to the above scheme, the thixotropic agent is fumed silica, particle size range 40-60um.
According to the above scheme, the defoaming agent is Bi Ke BYK-037 defoaming agent.
The phosphorous epoxy hardener synthetic route of the present invention:
Compared with prior art, the present invention have it is following the utility model has the advantages that
Component A uses phosphorous epoxy resin system, has certain flame retardant property.
Component B uses phosphorous epoxy hardener, it is severe to solve high temperature resistant epoxy adhesive curing process in room temperature curing
The shortcomings that quarter, not only increases adhesive temperature tolerance and mechanical property under the conditions of flame retardant property and room temperature curing and does not decline；Together
When sea water resistance dielectric behavior it is excellent.
By being used in compounding for inorganic filler and thixotropic agent, enables adhesive that there is fabulous sag resistance, improve
Convenience for construction, while the inorganic fillers such as expanded graphite alkene, zinc borate and antimony oxide have good smoke-suppressing.
The adhesive adhesive property is excellent, all has excellent adhesion to high energy surfaces such as metal material, polymer, and
Preparation method is simple, raw material are easy to get.
Specific embodiment
Following embodiment further illustrates technical solution of the present invention, but not as limiting the scope of the invention.
The present invention is as follows using the specific preparation process of phosphorous epoxy hardener:
Glycidol (12.5g, 0.169mol) is stirred together with 60mL tetrahydrofuran in 250mL round-bottomed flask.It will
The dry triethylamine (17.1g, 0.169mol) of distillation is added in solution, and solution is then cooled to 70 DEG C with ice bath.It is added
Cu2Cl2After (0.3g), the 40mL of phenyl dichloro phosphate (16.3g, 0.077mol) is added dropwise into reaction solution in 30 minutes
Tetrahydrofuran solution.Then, after 70 DEG C are kept for 2 hours, solution is kept 48 hours again at room temperature.With ice-cold NaOH water
Solution (2wt%) and distilled water filtering and collecting filter liquid, are then extracted with ethyl acetate three times.Extract liquor MgSO4It is dry, so
After be concentrated.Products therefrom is purified by column chromatography (using EA/ n-hexane 1/1 as eluant, eluent), and is stored in refrigerator.
Embodiment 1
Component A:
Component B:
651 epoxy hardener 80g
Fumed silica 10g
Bi Ke BYK-037 defoaming agent 5g
The preparation of component A: by SQEP-803EK75 type phosphorous epoxy resin, ammonium polyphosphate (APP), carbon forming agent Ji Wusi
Alcohol (PER), foaming agent melamine (MEL), expanded graphite alkene, zinc borate, antimony oxide, fumed silica and Bi Ke BYK-
037 defoaming agent stands defoaming under the conditions of 25-30 DEG C after uniform stirring.
The preparation of B component: by 651 epoxy hardeners, fumed silica and Bi Ke BYK-037 defoaming agent at 25-30 DEG C
Under the conditions of defoaming is stood after uniform stirring；
The component A obtained in the step and component B is uniformly mixed and can be constructed in 100:50 ratio.Room temperature is solid
It is tested after changing 3 days.
Embodiment 2
Component A:
Component B:
Phosphorous epoxy hardener 80g
Fumed silica 10g
Bi Ke BYK-037 defoaming agent 5g
The preparation of component A: by SQEP-803EK75 type phosphorous epoxy resin, ammonium polyphosphate (APP), carbon forming agent Ji Wusi
Alcohol (PER), foaming agent melamine (MEL), expanded graphite alkene, zinc borate, antimony oxide, fumed silica and Bi Ke BYK-
037 defoaming agent stands defoaming under the conditions of 25-30 DEG C after uniform stirring.
The preparation of B component: by phosphorous epoxy hardener, fumed silica and Bi Ke BYK-037 defoaming agent at 25-30 DEG C
Under the conditions of defoaming is stood after uniform stirring；
The component A obtained in the step and component B is uniformly mixed and can be constructed in 100:50 ratio.Room temperature is solid
It is tested after changing 3 days.
Embodiment 3
Component A:
Component B:
Phosphorous epoxy hardener 80g
Fumed silica 10g
Bi Ke BYK-037 defoaming agent 5g
The preparation of component A: by SQEP-803EK75 type phosphorous epoxy resin, ammonium polyphosphate (APP), carbon forming agent Ji Wusi
Alcohol (PER), foaming agent melamine (MEL), expanded graphite alkene, zinc borate, antimony oxide, fumed silica and Bi Ke BYK-
037 defoaming agent stands defoaming under the conditions of 25-30 DEG C after uniform stirring.
The preparation of B component: by phosphorous epoxy hardener, fumed silica and Bi Ke BYK-037 defoaming agent at 25-30 DEG C
Under the conditions of defoaming is stood after uniform stirring；
The component A obtained in the step and component B is uniformly mixed and can be constructed in 100:50 ratio.Room temperature is solid
It is tested after changing 3 days.
Embodiment 4
Component A:
Component B:
Phosphorous epoxy hardener 80g
Fumed silica 10g
Bi Ke BYK-037 defoaming agent 5g
The preparation of component A: by SQEP-803EK75 type phosphorous epoxy resin, ammonium polyphosphate (APP), carbon forming agent Ji Wusi
Alcohol (PER), foaming agent melamine (MEL), expanded graphite alkene, zinc borate, antimony oxide, fumed silica and Bi Ke BYK-
037 defoaming agent stands defoaming under the conditions of 25-30 DEG C after uniform stirring.
The preparation of B component: by phosphorous epoxy hardener, fumed silica and Bi Ke BYK-037 defoaming agent at 25-30 DEG C
Under the conditions of defoaming is stood after uniform stirring；
The component A obtained in the step and component B is uniformly mixed and can be constructed in 100:50 ratio.Room temperature is solid
It is tested after changing 3 days.
Embodiment 5
Component A:
Component B:
Phosphorous epoxy hardener 100g
Fumed silica 10g
Bi Ke BYK-037 defoaming agent 5g
The preparation of component A: by SQEP-803EK75 type phosphorous epoxy resin, ammonium polyphosphate (APP), carbon forming agent Ji Wusi
Alcohol (PER), foaming agent melamine (MEL), expanded graphite alkene, zinc borate, antimony oxide, fumed silica and Bi Ke BYK-
037 defoaming agent stands defoaming under the conditions of 25-30 DEG C after uniform stirring.
The preparation of B component: by phosphorous epoxy hardener, fumed silica and Bi Ke BYK-037 defoaming agent at 25-30 DEG C
Under the conditions of defoaming is stood after uniform stirring；
The component A obtained in the step and component B is uniformly mixed and can be constructed in 100:50 ratio.Room temperature is solid
It is tested after changing 3 days.
The results are shown in Table 1 for the test performance of the embodiment of the present invention 1-5:
Table 1: the performance test results of 1-5 of the embodiment of the present invention
Specific embodiments of the present invention are described in the above.It is to be appreciated that the invention is not limited to
Above-mentioned particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this is simultaneously
Substantive content of the invention is not influenced.
Claims (8)
1. a kind of flame retardant epoxy adhesive peculiar to vessel, it is characterised in that including component A and B component；
The composition of the component A is calculated by weight as:
The composition of the component B is calculated by weight as:
Phosphorous epoxy hardener 60-80
Thixotropic agent 1-5
Defoaming agent 0.1-2.
2. flame retardant epoxy adhesive peculiar to vessel as described in claim 1, it is characterised in that the phosphorous epoxy resin is phosphorous DOPO
Epoxy resin.
3. flame retardant epoxy adhesive peculiar to vessel as described in claim 1, it is characterised in that the phosphorous epoxy hardener chemical formula are as follows:
4. flame retardant epoxy adhesive peculiar to vessel as described in claim 1, it is characterised in that the phosphorous epoxy hardener preparation method
It is as follows:
Glycidol is dissolved in tetrahydrofuran, triethylamine is added and is stirred to react and controls temperature at 70 DEG C or so；Cu is added2Cl2Afterwards
The reaction of phenyl dichloro phosphate is added dropwise；It is filtered after standing, collects filtrate, be extracted with ethyl acetate, collect extract liquor；It is dense after drying
Contracting, purifying obtain target product.
5. flame retardant epoxy adhesive peculiar to vessel as described in claim 1, it is characterised in that the fire-proof function component presses quality percentage
Number is calculated as:
Ammonium polyphosphate 50wt%；Carbon forming agent pentaerythrite 25-30wt%, foaming agent melamine 20-25wt%.
6. flame retardant epoxy adhesive peculiar to vessel as described in claim 1, it is characterised in that the inorganic filler is expanded graphite alkene, boron
One of sour zinc and antimony oxide or any mixing.
7. flame retardant epoxy adhesive peculiar to vessel as described in claim 1, it is characterised in that the thixotropic agent is fumed silica, grain
Diameter range is 40-60um.
8. flame retardant epoxy adhesive peculiar to vessel as described in claim 1, it is characterised in that the defoaming agent is Bi Ke BYK-037 defoaming
Agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811595160.XA CN109749682A (en) | 2018-12-25 | 2018-12-25 | A kind of flame retardant epoxy adhesive peculiar to vessel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811595160.XA CN109749682A (en) | 2018-12-25 | 2018-12-25 | A kind of flame retardant epoxy adhesive peculiar to vessel |
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| Publication Number | Publication Date |
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| CN109749682A true CN109749682A (en) | 2019-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811595160.XA Pending CN109749682A (en) | 2018-12-25 | 2018-12-25 | A kind of flame retardant epoxy adhesive peculiar to vessel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777980A (en) * | 2020-06-24 | 2020-10-16 | 步阳集团有限公司 | Adhesive for high-temperature ceramic blocking fireproof door |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111777980A (en) * | 2020-06-24 | 2020-10-16 | 步阳集团有限公司 | Adhesive for high-temperature ceramic blocking fireproof door |
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Application publication date: 20190514 |