CN109705312A - One kind is based on difunctional POSS high-temperature-resistant epoxy resin and its preparation and application - Google Patents
One kind is based on difunctional POSS high-temperature-resistant epoxy resin and its preparation and application Download PDFInfo
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Abstract
The present invention relates to one kind based on difunctional POSS high-temperature-resistant epoxy resin and its preparation and application.The resin Composition includes: amino, vinyl difunctional POSS 7.0%-26.0% and epoxy resin 93.0%-74.0% by mass fraction.Preparation method includes: to stir epoxy resin, and addition amino, the difunctional POSS solution of vinyl continue to stir, and evaporate, and is solidified for the first time, second of solidification.The resin has preferable thermal stability and mechanical property.
Description
Technical field
It is the invention belongs to epoxy resin composite material and its preparation method and application field, in particular to a kind of based on double function
Energy POSS high-temperature-resistant epoxy resin and its preparation method and application.
Background technique
Epoxy resin cured product has excellent comprehensive performance, and it is multiple to can be used as coating, adhesive, castable and fiber reinforcement
The materials such as the matrix resin of condensation material, therefore be widely used in aerospace, chemical industry, machinery, motor, ship, automobile, building etc.
Every field.Epoxy resin has excellent mechanics and adhesion property, while weatherability, corrosion resistance, electrical insulating property and mechanics
Functional, excellent comprehensive performance is widely used in the substrate of functional elastomer, however, the high temperature resistance of epoxy resin is
Problem to be solved.
Since POSS has special physico-chemical property, so that it has other common inorganic nanometers at polymer-modified aspect
The unrivaled advantage of material.In POSS epoxy resin cure to be applied to, then must have distinctive active function groups, that is, exist
Introduce active function groups on POSS molecule, the polyhedral each vertex of functionalization cage modle siloxanes connect organo-functional group can with it is more
Kind organic compound combines, and organic material is organically combined together with inorganic material, while playing the advantage of the two, to reach
To performance complement, the purpose of raising material comprehensive performance.Functionalized POSS can be introduced directly into macromolecular scaffold.It is this
Introducing is molecular level, is evenly distributed on entire composite material by covalent bond or organic compatibility between inorganic phase and polymer
In, reunion and the weak problem of two interphase interface binding forces there is no inorganic particulate, and each apex angle of silicon cage can introduce
Different reactive functional groups, so the high functional group densities that there are other curing agent to be extremely difficult to for it, effectively improve solidification ring
The hot property of oxygen resin.
A kind of " the preparation side of epoxy resin-POSS hybrid resin and its composite material Chinese patent 201210193979.X
Using unique monoisocyanates base cage model sesquialter silicon oxygen by graft modification epoxy molecule in method ", with molecularly dispersed structure
Copolymerization is not participated in as crosslinking points on molecular resin main chain, obtains high heat resistance, the Advanced Electronic Encapsulating substrate of low dielectric is used
Resin.Hybrid resin after fixed line has smaller intermolecular distance and more segmental flow ability.Chinese patent
" 201410444674.0 the preparation method that one kind is based on modified epoxy-POSS environment friendly flame-retardant epoxy resin composite material "
It is middle that epoxy resin and modified epoxy-POSS are completely dissolved in the resin adhesive liquid that 80wt.% is made in solvent together；It will solidification
Agent and curing accelerator are dissolved completely in solution；Resin adhesive liquid and mixed liquor are mixed, then mixed liquor is heated,
Curing molding is carried out using two step temperature-raising methods, obtains the hybridization epoxy resin composite material of suspended side chain POSS, obtains preferably resistance
Fire performance.Chinese patent 201711040548.9 " a kind of eight arm epoxy resin of POSS base organic-inorganic hydridization and its preparation side
In method ", using octavinyl-POSS, it is prepared for the eight arm epoxy resin of POSS base organic-inorganic hydridization that epoxy group is end group.
These are the modification technologies of single function group POSS, are difficult to realize the requirement of multifunctional modification.
Summary of the invention
Technical problem to be solved by the invention is to provide one kind to be based on difunctional POSS high-temperature-resistant epoxy resin and its system
Preparation Method and application, to overcome the defect of conventional epoxy curing agent heat resistance and poor mechanical property in the prior art.
The present invention passes through the MOLECULE DESIGN of bi-functional group and inorganic nano POSS core, mainly takes into account material mechanical performance
With comprehensively considering for high temperature resistance, forms difunctional POSS with different performance compounding ingredients respectively and be chemically combined, improve material
Expect interface performance and stability, it is more preferable to improve material hot property.
One kind of the invention is based on difunctional POSS epoxy resin, and component includes: amino according to mass fraction, and vinyl is double
Function POSS 7.0%-26.0% and epoxy resin 93.0%-74.0%.
The molecular formula of the difunctional POSS of the amino, vinyl are as follows: (NH2)n-POSS-(CH2=CH-R)m, 2≤n in formula
≤ 8, m >=1；Epoxy resin is bisphenol A type epoxy resin E51.
It is described based on difunctional POSS epoxy resin further include toughener 8~12%, toughener is liquid nitrile rubber
AIBN。
A kind of preparation method based on difunctional POSS epoxy resin of the invention, comprising:
(1) in a solvent by amino, the difunctional POSS dissolution of vinyl, obtaining NV-POSS mass fraction is 15-25%'s
Solution, the solution are passed through nitrogen, make system in N2Under atmosphere, 0-5 DEG C of cryo-conservation；
(2) epoxy resin is stirred, NV-POSS solution in step (1) is added and continues to stir, rotary evaporation in vacuo, first
Secondary solidification, second of solidification, obtains based on difunctional POSS epoxy resin, wherein being pressed based on difunctional POSS epoxy resin ingredient
It include: NV-POSS 7.0%-26.0% and epoxy resin 93.0%-74.0% according to mass fraction.
The molecular formula of amino, the difunctional POSS of vinyl in the step (1) are as follows: (NH2)n-POSS-(CH2=CH-R)m,
2≤n≤8 in formula, m >=1.
Solvent is acetone in the step (1).
Toughener AIBN is added in the step (1) in NV-POSS solution, AIBN is being based on difunctional POSS epoxy resin
In mass fraction be 8~12%.
Epoxy resin is bisphenol A type epoxy resin E51 in the step (2).
Whipping temp is 55 DEG C -65 DEG C in the step (2), mixing time 8min-1h.
Continuing whipping temp in the step (2) is 55 DEG C -65 DEG C, and continuation mixing time is 25min-35min.
Rotating evaporation temperature is 50 DEG C -95 DEG C in the step (2)；Time is 1-3min.
First time solidification temperature is 90 DEG C -110 DEG C in the step (2), and curing time first time is 3h-5h.
Second of solidification temperature is 140 DEG C -160 DEG C in the step (2), and second of curing time is 2h-7h.
A kind of application based on difunctional POSS epoxy resin of the invention.
As curing agent functional group, vinyl can carry out the further reinforcement of thermal polymerization crosslinking progress and mention amino in the present invention
Strong mechanical performance also can be used as the chemical crosslinking of the toughener with double bond, realize toughener and resin matrix configuration chemical bonds,
It plays and further enhances the heat of material and the effect of mechanical stability.
Beneficial effect
The present invention has the amido POSS of branch and active amine by the synthesis to end group POSS, preparation, obtains hot steady
Qualitative good curing agent, is applied in the solidification of epoxide resin material, can be improved the heat resistance of epoxy resin, be made it have
Preferable thermal stability improves the mechanical property of composite material, improves the low temperature impact properties that composite material is higher than room temperature.This is multiple
Condensation material maximum glass transition temperature is up to 250 DEG C, and for softening point temperature o'clock up to 300 DEG C, decomposition temperature is up to 376 DEG C.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The preparation of NV-POSS acetone soln.Under nitrogen range, NV-POSS is dissolved in acetone, obtains NV-POSS matter
The solution that score is 20% is measured, 0-5 DEG C of cryo-conservation is placed in.((NH2)n-POSS-(CH2=CH-R)m, n=4, m=4 in formula)
Embodiment 2
The preparation of NV-POSS cured epoxy resin.Bisphenol A type epoxy resin E51 is stirred into 10min, system at 60 DEG C
It has preferable mobility, adds in embodiment 1 after NH-POSS solution, system has bubble spilling, continues to stir 30min (nothing
Bubble overflows), good fluidity is presented in system, is transferred to 90 DEG C of revolvings and vacuumizes 2min, prepares bubble-free resin, shift rapidly
Into baking oven, 100 DEG C of placement 4h in convection oven continue to solidify 6h at 150 DEG C, it is solid to obtain NH-POSS after taking out batten
Change epoxide resin material, wherein NH-POSS mass fraction is 7.5%, E51 mass point in NH-POSS cured epoxy resin material
Number is 92.5%.
Embodiment 3
The hot property of NV-POSS cured epoxy resin.The mass fraction of system composition is respectively as follows: according to NH-POSS content
22%, E51 epoxy resin content 78% is added 20% acetone solvent, stirs at 60 DEG C after two components and solvent mixing
30min, then rotary evaporation in vacuo removes acetone at 50 DEG C, and the blended liquid of certain viscosity is placed in polytetrafluoroethylene (PTFE) template,
100 DEG C of placement 4h in convection oven continue to solidify 2h at 150 DEG C, obtain NV-POSS cured epoxy resin after taking out batten
Material.Its Thermal Parameter is tested to cured epoxy resin is obtained.The results show that the vitrifying of NV-POSS cured epoxy resin
Transition temperature reaches 164 DEG C, and compare other curing agent, and NV-POSS cured epoxy resin glass transition temperature improves, together
When NV-POSS cured epoxy resin thermal decomposition temperature be up to 362 DEG C.
Embodiment 4
The hot property of NV-POSS cured epoxy resin.NV-POSS cured epoxy resin material is prepared according to embodiment 3, it will
" continue to solidify 2h at 150 DEG C " in embodiment 3 to be changed to " continuing to solidify 4h at 150 DEG C ", remaining is same as Example 3, obtains NV-
POSS cured epoxy resin material.Its Thermal Parameter is tested to the cured epoxy resin of acquisition.The results show that NV-POSS is solid
The glass transition temperature for changing epoxy resin reaches 183 DEG C, compares in 150 DEG C of solidification 2h, solidifies 4h at 150 DEG C and solidifies ring
The glass transition temperature of oxygen resin increases, while the thermal decomposition temperature of NV-POSS cured epoxy resin is increased to 364 DEG C.
Embodiment 5
The hot property of NV-POSS cured epoxy resin.NV-POSS cured epoxy resin material is prepared according to embodiment 3, it will
" continue to solidify 2h at 150 DEG C " in embodiment 3 to be changed to " continuing to solidify 6h at 150 DEG C ", remaining is same as Example 3, obtains NV-
POSS cured epoxy resin material.Its Thermal Parameter is tested to cured epoxy resin is obtained.The results show that NV-POSS solidifies
The glass transition temperature of epoxy resin reaches 233 DEG C, and compare other curing agent, NV-POSS cured epoxy resin vitrifying
Temperature tool has a very significant increase, while the thermal decomposition temperature of NV-POSS cured epoxy resin is up to 376 DEG C, has very great Cheng
The raising of degree.
Embodiment 6
The mechanical property of NV-POSS cured epoxy resin.Polyhydroxy butyronitrile rubber is added in NV-POSS curing system composition
Glue (ATBN), ATBN content are system weight 10%, NV-POSS 15.3%, when E51 epoxy resin 74.7%, by embodiment 3
In " continue at 150 DEG C solidify 2h " be changed to " continuing to solidify 6h at 150 DEG C ", remaining is same as Example 3, obtains ATBN/NV-
POSS cured epoxy resin material.Its mechanical energy parameter is tested to cured epoxy resin is obtained.The results show that ATBN/NV-POSS
The bending modulus of cured epoxy resin is up to 3.3Gpa, and compare other curing agent, ATBN/NV-POSS cured epoxy resin
Bending modulus has a very significant increase.
Embodiment 7
The hot property of NV-POSS/ epoxy resin composite material.The quality point of NV-POSS/ epoxy resin composite material composition
Number is respectively as follows: according to NV-POSS content 16%, E51 epoxy resin content 84%, " will continue to solidify at 150 DEG C in embodiment 3
2h " is changed to " continuing to solidify 6h at 150 DEG C ", remaining is same as Example 3, obtains NV-POSS cured epoxy resin material.To obtaining
It obtains cured epoxy resin and tests its Thermal Parameter.The results show that the glass transition temperature of NV-POSS cured epoxy resin reaches
To 190 DEG C, decomposition temperature reaches 362 DEG C, still better than other class amine based curatives.
Comparative example 1
Using traditional E51 epoxy resin and curing agent E100, according to E51 component 84%, E100 component 16% is mixed, is adopted
With the same preparation condition of example 7, the results show that the glass transition temperature of cured epoxy resin reaches 122 DEG C, decomposition temperature
Reach 332 DEG C.It can be seen that being greatly improved using NV-POSS curing agent material glass temperature, increase rate depends on formula, most
It is big improve the present invention study the result is that 233 DEG C.
Claims (10)
1. one kind is based on difunctional POSS epoxy resin, which is characterized in that component includes: amino, vinyl according to mass fraction
Difunctional POSS 7.0%-26.0% and epoxy resin 93.0%-74.0%.
2. epoxy resin according to claim 1, which is characterized in that the molecule of the difunctional POSS of the amino, vinyl
Formula are as follows: (NH2)n-POSS-(CH2=CH-R)m, 2≤n≤8 in formula, m >=1；Epoxy resin is bisphenol A type epoxy resin E51.
3. epoxy resin according to claim 1, which is characterized in that described to further include based on difunctional POSS epoxy resin
Toughener 8~12%, toughener are liquid nitrile rubber AIBN.
4. a kind of preparation method based on difunctional POSS epoxy resin, comprising:
(1) in a solvent by amino, the difunctional POSS dissolution of vinyl, obtaining NV-POSS mass fraction is the molten of 15-25%
Liquid；
(2) epoxy resin is stirred, NV-POSS solution in step (1) is added and continues to stir, rotary evaporation in vacuo is solid for the first time
Change, second of solidification is obtained based on difunctional POSS epoxy resin, wherein pressing quality based on difunctional POSS epoxy resin ingredient
Score includes: NV-POSS 7.0%-26.0% and epoxy resin 93.0%-74.0%.
5. according to the method described in claim 4, it is characterized in that, amino in the step (1), the difunctional POSS of vinyl
Molecular formula are as follows: (NH2)n-POSS-(CH2=CH-R)m, 2≤n≤8 in formula, m >=1；Solvent is acetone.
6. according to the method described in claim 4, it is characterized in that, toughener is added in NV-POSS solution in the step (1)
AIBN, AIBN are being 8~12% based on the mass fraction in difunctional POSS epoxy resin.
7. according to the method described in claim 4, it is characterized in that, in the step (2) whipping temp be 55 DEG C -65 DEG C, stir
Mixing the time is 8min-1h.
8. according to the method described in claim 4, it is characterized in that, rotating evaporation temperature is 50 DEG C -95 in the step (2)
DEG C, time 1-3min；First time solidification temperature is 90 DEG C -110 DEG C, and curing time first time is 3h-5h.
9. according to the method described in claim 4, it is characterized in that, in the step (2) second solidification temperature be 140 DEG C-
160 DEG C, second of curing time is 2h-7h.
10. a kind of application as described in claim 1 based on difunctional POSS epoxy resin.
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| CN201811591836.8A CN109705312A (en) | 2018-12-25 | 2018-12-25 | One kind is based on difunctional POSS high-temperature-resistant epoxy resin and its preparation and application |
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| CN110317561A (en) * | 2019-05-18 | 2019-10-11 | 福建省昌德胶业科技有限公司 | A kind of high-strength endurance type epoxy resin structural adhesive and preparation method thereof |
| CN111205597A (en) * | 2020-02-28 | 2020-05-29 | 厦门市宜帆达新材料有限公司 | High-performance epoxy resin and preparation method thereof |
| CN115093674A (en) * | 2022-06-10 | 2022-09-23 | 佛山萤鹤新材料有限公司 | Modified epoxy resin for LED packaging and preparation method thereof |
| CN115850714A (en) * | 2022-12-13 | 2023-03-28 | 东华大学 | POSS (polyhedral oligomeric silsesquioxane) modified nitrile rubber compound as well as preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317561A (en) * | 2019-05-18 | 2019-10-11 | 福建省昌德胶业科技有限公司 | A kind of high-strength endurance type epoxy resin structural adhesive and preparation method thereof |
| CN111205597A (en) * | 2020-02-28 | 2020-05-29 | 厦门市宜帆达新材料有限公司 | High-performance epoxy resin and preparation method thereof |
| CN115093674A (en) * | 2022-06-10 | 2022-09-23 | 佛山萤鹤新材料有限公司 | Modified epoxy resin for LED packaging and preparation method thereof |
| CN115850714A (en) * | 2022-12-13 | 2023-03-28 | 东华大学 | POSS (polyhedral oligomeric silsesquioxane) modified nitrile rubber compound as well as preparation method and application thereof |
| CN115850714B (en) * | 2022-12-13 | 2024-03-22 | 东华大学 | POSS modified nitrile rubber compound and preparation method and application thereof |
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Application publication date: 20190503 |