CN106751473B - A method of preparing selfreparing epoxy resin composite material using mesoporous SBA-15 - Google Patents
A method of preparing selfreparing epoxy resin composite material using mesoporous SBA-15 Download PDFInfo
- Publication number
- CN106751473B CN106751473B CN201611052183.7A CN201611052183A CN106751473B CN 106751473 B CN106751473 B CN 106751473B CN 201611052183 A CN201611052183 A CN 201611052183A CN 106751473 B CN106751473 B CN 106751473B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- mass parts
- liquid
- resin composite
- sba
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 6
- 239000013335 mesoporous material Substances 0.000 claims abstract description 18
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000007711 solidification Methods 0.000 claims abstract description 6
- 230000008023 solidification Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 21
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 13
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011984 grubbs catalyst Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000004035 construction material Substances 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 6
- 239000003094 microcapsule Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000004092 self-diagnosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a kind of methods preparing selfreparing epoxy resin composite material using mesoporous material SBA-15.Mesoporous material SBA-15 is added in the monomer mixture of dicyclopentadiene and styrene and is saturated absorption, it is subsequently added in the mixed liquor being made of epoxy resin E51, curing agent diethylenetriamine and Grubbs catalyst, ultrasonic vibration after manual mixing, it is allowed to after mixing, bubble-free to be evacuated to, it pours into mold, the epoxy resin composite material with multiple self-repair function is obtained after solidification.The present invention can effectively improve the problem of local damage and micro-crack of basis material, to make security risk be minimized；To a certain extent can restorer performance, increase the service life of material, it is expected to be widely used in fields such as coating, construction material and composite materials.
Description
Technical field
The technical field of the invention is polymer matrix composite selfreparing field, utilizes Jie of saturation absorption renovation agent
Porous materials prepare epoxy resin/SBA-15 self-repair materials.
Background technology
Self-repair material is the intelligent composite for having self diagnosis, self-repair function, by imitating life system damage
The principle of healing enables the internal outside exergy dissipation of composite material to injure micro-crack and carries out selfreparing, to make hidden danger be eliminated, material
The intensity enhancing of material and materials'use service life extend.
Dicyclopentadiene（DCPD）Consolidant common in self-repair material, usually DCPD is wrapped in microcapsules plus
Enter in resin matrix.When material generates crack, crack leads to microcapsules rupture, DCPD therein flow out in matrix
After the contact of Grubbs catalyst, ring-opening metathetic polymerization reaction can occur（ROMP）, PDCPD is generated, to repair gap, is played certainly
The effect of reparation.But there is crack again in the position once repaired, it, cannot be again since the DCPD in microcapsules all flows out
Material is repaired.
Mesoporous material is the porous material that the three-dimensional net structure that abundant tiny holes are constituted is distributed in a kind of inside,
Aperture is in large pore material（> 50nm）And poromerics（< 2nm）Between, since its unique texture makes mesoporous material have pole
The characteristics such as high specific surface, adjustable aperture, orderly duct, good stability and narrow pore-size distribution, by more next
The concern of more researchers.Mesoporous material has a wide range of applications in fields such as catalysis, separation, biology, medicine and materials.
Mesoporous material SBA-15 has two-dimentional hexagonal hole road structure, can adsorb consolidant DCPD, if saturation adsorbed
The mesoporous material of DCPD is introduced into resin matrix, when being cracked in resin matrix, due to absorption consolidant SBA-15 by
DCPD is gradually released, so as to be effectively improved the local damage and micro-crack of matrix, while repeatedly crackle can be repaired,
And then greatly prolong the service life of material.
Invention content
Local damage and micro-crack are generated in order to effectively solve material internal or surface, using traditional microcapsules dummy
System cannot multiple selfreparing the problem of, the present invention provide it is a kind of using mesoporous material SBA-15 absorption consolidant after polymer is added
In matrix, using its slow-release function, to obtain the method that can carry out multiple selfreparing.
The specific steps are：
（1）By dicyclopentadiene（DCPD）With styrene by volume 9:1 is mixed, and monomer mixture is obtained（Referred to as
For DS liquid）.
（2）By 1 ~ 100 mass parts step（1）Gained DS liquid is added in 1 ~ 10 mass parts mesoporous material SBA-15, saturation
Absorption 2 hours, is filtered to remove extra DS liquid.
（3）By 100 mass parts epoxy resin E51,10 mass parts curing agent diethylenetriamines（DETA）With 0.01 ~ 1 mass
Part Grubbs catalyst mixing, obtains mixed liquor.
（4）By 1 ~ 100 mass parts step（2）The mesoporous material of gained saturation absorption DS liquid is added to step（3）Gained is mixed
It closes in liquid, ultrasonic vibration after manual mixing is allowed to after mixing, and bubble-free to be evacuated to is poured into mold, after solidification
To the epoxy resin composite material with self-repair function.
Raw material described above are technical grade.
The invention has the characteristics that：
1. raw material sources are extensive, cheap to be easy to get.
2. operation is fairly simple, disposable.
3. repair rate is higher obtained by this method, and being capable of multiple selfreparing.
Specific implementation mode
Raw material as described below are technical grade.
Embodiment 1：
（1）By dicyclopentadiene（DCPD）It is mixed with styrene（Volume ratio 9:1）, obtain monomer mixture（Referred to as
For DS liquid）.
（2）By 2.25g steps（1）Gained DS liquid is added in 0.30 g mesoporous material SBA-15s, saturation absorption 2 hours,
It is filtered to remove extra DS liquid.
（3）6.0 g epoxy resin E51,0.6 g curing agent diethylenetriamine and 0.0023 g Grubbs catalyst are mixed
Close to obtain mixed liquor.
（4）By step（2）The mesoporous material of gained saturation absorption DS liquid is added to step（3）In gained mixed liquor, by hand
Ultrasonic vibration after mixing is allowed to after mixing, and bubble-free to be evacuated to is poured into mold, and repair rate is obtained after solidification and is
90.8% or so epoxy resin composite material.
Embodiment 2：
（1）By dicyclopentadiene（DCPD）It is mixed with styrene（Volume ratio 9:1）, obtain monomer mixture（Referred to as
For DS liquid）.
（2）1.35 gDS liquid are added in 0.18 g mesoporous material SBA-15s, saturation absorption 2 hours is filtered to remove more
Remaining DS liquid.
（3）6.0 g epoxy resin E51,0.6 g curing agent diethylenetriamine and 0.0014 g Grubbs catalyst are mixed
Close to obtain mixed liquor.
（4）By step（2）The mesoporous material of gained saturation absorption DS liquid is added to step（3）In gained mixed liquor, by hand
Ultrasonic vibration after mixing is allowed to after mixing, and bubble-free to be evacuated to is poured into mold, and repair rate is obtained after solidification and is
84.3% or so epoxy resin composite material.
Embodiment 3：
（1）By dicyclopentadiene（DCPD）It is mixed with styrene（Volume ratio 9:1）, obtain monomer mixture（Referred to as
For DS liquid）.
（2）2.25 g DS liquid are added in 0.30 g mesoporous material SBA-15s, saturation absorption 2 hours is filtered to remove
Extra DS liquid.
（3）6.0 g epoxy resin E51,0.6 g curing agent diethylenetriamine and 0.009 g Grubbs catalyst are mixed
Obtain mixed liquor.
（4）By step（2）The mesoporous material of gained saturation absorption DS liquid is added to step（3）In gained mixed liquor, by hand
Ultrasonic vibration after mixing is allowed to after mixing, and bubble-free to be evacuated to is poured into mold, and repair rate is obtained after solidification and is
92.3% or so epoxy resin composite material, secondary repair rate reach 55.8% or so.
Claims (1)
1. a kind of method preparing selfreparing epoxy resin composite material using mesoporous SBA-15, it is characterised in that specific steps
For：
（1）By dicyclopentadiene and styrene by volume 9:1 is mixed, and is obtained monomer mixture and is referred to as DS liquid；
（2）By 1 ~ 100 mass parts step（1）Gained DS liquid is added in 1 ~ 10 mass parts mesoporous material SBA-15, saturation absorption 2
Hour, it is filtered to remove extra DS liquid；
（3）100 mass parts epoxy resin E51,10 mass parts curing agent diethylenetriamines and 0.01 ~ 1 mass parts Grubbs are urged
Agent mixes, and obtains mixed liquor；
（4）By 1 ~ 100 mass parts step（2）The mesoporous material of gained saturation absorption DS liquid is added to step（3）Gained mixed liquor
In, ultrasonic vibration after manual mixing is allowed to after mixing, and bubble-free to be evacuated to is poured into mold, had after solidification
There is the epoxy resin composite material of self-repair function；
Raw material described above are technical grade.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611052183.7A CN106751473B (en) | 2016-11-25 | 2016-11-25 | A method of preparing selfreparing epoxy resin composite material using mesoporous SBA-15 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611052183.7A CN106751473B (en) | 2016-11-25 | 2016-11-25 | A method of preparing selfreparing epoxy resin composite material using mesoporous SBA-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106751473A CN106751473A (en) | 2017-05-31 |
| CN106751473B true CN106751473B (en) | 2018-11-06 |
Family
ID=58912431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611052183.7A Active CN106751473B (en) | 2016-11-25 | 2016-11-25 | A method of preparing selfreparing epoxy resin composite material using mesoporous SBA-15 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106751473B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509298A (en) * | 2001-02-13 | 2004-06-30 | ����ŵ˹��ѧ���»� | Multifunctional autonomically healing composite material |
| CN103540284A (en) * | 2013-09-26 | 2014-01-29 | 金发科技股份有限公司 | Sealant for self-repair and leak prevention of storage battery, and preparation method thereof |
| CN105038502A (en) * | 2015-07-17 | 2015-11-11 | 南通南京大学材料工程技术研究院 | Self-healing epoxy powdery coating containing microcapsule and preparation method thereof |
-
2016
- 2016-11-25 CN CN201611052183.7A patent/CN106751473B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1509298A (en) * | 2001-02-13 | 2004-06-30 | ����ŵ˹��ѧ���»� | Multifunctional autonomically healing composite material |
| CN103540284A (en) * | 2013-09-26 | 2014-01-29 | 金发科技股份有限公司 | Sealant for self-repair and leak prevention of storage battery, and preparation method thereof |
| CN105038502A (en) * | 2015-07-17 | 2015-11-11 | 南通南京大学材料工程技术研究院 | Self-healing epoxy powdery coating containing microcapsule and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106751473A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102702688B (en) | Preparation method of bisphenol-A epoxy resin/attapulgite nano composite material | |
| JP2013516747A5 (en) | ||
| BRPI0507139A (en) | porous cellulose aggregate, process for producing the same, and molded product composition | |
| RU2013128370A (en) | METHOD FOR PRODUCING UNITS FROM CEMENT COMPOSITIONS | |
| CN106866106A (en) | A kind of preparation method of silicon dioxide silica aerogel composite material | |
| CN110950603B (en) | High-strength anti-crack concrete and preparation method thereof | |
| CN105505400B (en) | A kind of soil-solidified-agent and preparation method thereof | |
| DE502007006695D1 (en) | METHOD FOR PRODUCING WATER ABSORBING POLYMER PARTICLES BY POLYMERIZATION OF DROPS OF A MONOMER SOLUTION | |
| CN106751473B (en) | A method of preparing selfreparing epoxy resin composite material using mesoporous SBA-15 | |
| CN105038496A (en) | Nanometer Al2O3 composite aerosil thermal-insulation heat-preserving paint and preparation method thereof | |
| CN107649092B (en) | Clay matrix type adsorbent and preparation method thereof | |
| CN110305492B (en) | Emulsified asphalt with improved strength after curing | |
| CN104371626A (en) | Epoxy resin adhesive for potting PVDF hollow fiber membrane and preparation method of epoxy resin adhesive | |
| CN111072342B (en) | Recycled aggregate pervious concrete with increased porosity and preparation method thereof | |
| CN106396575B (en) | A kind of nitrogen fertilizer slow-releasing type plants raw rubber gel material and preparation method thereof | |
| CN105060782A (en) | Enhanced polymer concrete and non-impregnation preparation method | |
| CN105312034A (en) | Preparation method for high-specific-surface magnetic resin ball | |
| CN109647197A (en) | A kind of casting formula of the component of hollow fiber nanofiltration membrane at room temperature | |
| CN104478340A (en) | Low-cost concrete preparation method | |
| RU2016125486A (en) | METHOD FOR OBTAINING TIRE PROTECTORS, RUBBER MIXTURE, CROWN ZONE AND WINTER TIRE | |
| CN104987121B (en) | Nutritional foaming and coagulating grass planting building block and preparation method therefor | |
| CN108176803A (en) | The preparation method of absorbent-type precoated sand is split in a kind of resistance to compression | |
| CN102531663B (en) | Porous silica ceramic with double layers of pores and preparation method thereof | |
| CN104984735A (en) | Adsorption resin | |
| CN106751474B (en) | The method for preparing selfreparing epoxy resin composite material using modified mesoporous SBA-15 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170531 Assignee: Guangxi Aigui Intelligent Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2023980044282 Denomination of invention: A method for preparing self-healing epoxy resin composite materials using mesoporous SBA-15 Granted publication date: 20181106 License type: Common License Record date: 20231025 |
|
| EE01 | Entry into force of recordation of patent licensing contract |