CN105131531A - Triblock copolymer modified epoxide resin and preparing method thereof - Google Patents
Triblock copolymer modified epoxide resin and preparing method thereof Download PDFInfo
- Publication number
- CN105131531A CN105131531A CN201510631505.2A CN201510631505A CN105131531A CN 105131531 A CN105131531 A CN 105131531A CN 201510631505 A CN201510631505 A CN 201510631505A CN 105131531 A CN105131531 A CN 105131531A
- Authority
- CN
- China
- Prior art keywords
- pcl
- pdms
- epoxy resin
- triblock copolymer
- structural formula
- 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.)
- Pending
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention discloses a preparing method of PCL-b-PDMS-b-PCL triblock copolymer modified epoxide resin. Epoxy resin, curing agents and PCL-b-PDMS-b-PCL triblock copolymers with different mass ratios are evenly mixed in a hot melting mode and cured. The preparing method is characterized in that raw materials include, by mass, 100 parts of epoxy resin, 30-50 parts of curing agent and 10-50 parts of PCL-b-PDMS-b-PCL, and a PCL-b-PDMS-b-PCL modified epoxy resin system is obtained. The preparing method is simple in technological process and easy to operate, reaction conditions are easy to control, the reaction raw materials are easy to obtain, the modified epoxy resin has good heat resistance, the requirement of the epoxy resin in the field of space flight and aviation is met, and the application range of the epoxy resin is further expanded.
Description
Technical field
The invention belongs to modified epoxy field, disclose a kind of preparation method of triblock copolymer PCL-b-PDMS-b-PCL modified epoxy.
Background technology
Epoxy resin is the organic compound containing epoxide group in molecule, there are after solidification good physics, chemical property, dielectric properties and chemical stability etc., have excellent cohesive strength to the surface of metal and non-metallic material, it is increasingly extensive in the application of sizing agent, electronic apparatus, aerospace and field of compound material.
Recently, people recognize that the orderly or disordered structure formed on nanoscale contributes to the interaction optimized further between epoxy resin-base and properties-correcting agent in epoxy resin blend, thus can improve its physicals better.Nanoparticle is owing to having nanometer size effect, and surface-interface effect, can improve mechanical property and the thermal characteristics of epoxy resin well.By physics or chemisorption between nanoparticle and epoxy resin, define special interfacial layer, when material is by stress, this interfacial layer can play the effect suppressing crazing to increase, thus improves the fracture toughness property of material.
Segmented copolymer refers to by the particular polymer having the polymer segment of two or more different in kind to be connected with covalent linkage.The advantages such as polydimethylsiloxane (PDMS) has thermostability, resistance to oxidation, weather-proof and cold property good, surface energy is low, therefore be the focus that development in recent years is got up with polydimethylsiloxane--modified epoxy resin, but the poor problem of the consistency of PDMS and epoxy resin still exist.
The present invention adopts a kind of triblock polymer PCL-b-PDMS-b-PCL epoxy resin to be carried out to the method for modification, to improve its toughness to meet its requirement in field of aerospace.
Summary of the invention
the technical problem solved
Invention introduces the triblock polymer containing polydimethylsiloxane (PDMS) segment, another section is and the polycaprolactone of epoxy resin compatibility (PCL).PDMS before curing after be all inconsistent with epoxy resin, therefore comprising with the segmented copolymer of the segment of epoxy resin compatibility (such as PCL) and PDMS segment is form nanostructure with the mechanism of self-assembly in the epoxy.The present invention has used the method for ring-opening polymerization, and design and synthesis PCL-b-PDMS-b-PCL triblock copolymer, has then prepared the thermosetting resin with nanostructure by this segmented copolymer and epoxy blend.The object of the invention is to the type and the size that are controlled nanostructure disperse phase by adjustment block concentration, resistance to elevated temperatures and the toughness of epoxy resin is improved, with the application requiring of satisfied high performance structures resin material of new generation in the field such as aerospace, electric industry by adding a small amount of PCL-b-PDMS-b-PCL.
technical scheme
Epoxy resin used in the present invention is 4,5-oxepane-1,2-dioctyl phthalate 2-glycidyl ester (TDE-85), belongs to cycloaliphatc glycidyl fat trifunctional epoxy resin, as shown in structural formula 1:
Structural formula 1TDE-85.
Solidifying agent used in the present invention is amine curing agent: DDS (being called for short DDS), as shown in structural formula 2:
Structural formula 2DDS.
Block polymer used in the present invention is PCL-b-PDMS-b-PCL, as shown in structural formula 3:
Structural formula 3PCL-b-PDMS-b-PCL.
Object of the present invention is achieved through the following technical solutions, and its feature is as follows:
Object of the present invention is achieved through the following technical solutions, and its feature is as follows:
Be cured after the TDE-85 of different mass proportioning, DDS and PCL-b-PDMS-b-PCL melt compounding is even.Technical characteristic of the present invention is that composition of raw materials is by mass: epoxy resin TDE-85 is 100 parts (mass fractions), solidifying agent DDS is 30 ~ 50 parts (mass fractions), PCL-b-PDMS-b-PCL is 10 ~ 50 parts (mass fractions), obtains a kind of CL-b-PDMS-b-PCL modification TDE-85/DDS resin system.
Preparation method's technical process involved in the present invention is simple, operation is easy to realization, reaction conditions is easy to control, reaction raw materials is easy to obtain, epoxy resin through PCL-b-PDMS-b-PCL modification possesses good performance, meet its requirement in fields such as space flight and aviation, the range of application of epoxy resin is obtained and further widens.
Embodiment
For ease of understanding the present invention further, the following example has set forth details particularly, but embodiments of the present invention are not limited thereto.
Embodiment 1:
TDE-85, DDS, PCL-b-PDMS-b-PCL of taking are respectively 10g, 3g, 1g.By three kinds of components abundant hot melt mixing at 130 DEG C, in vacuum drying oven, place 24h remove bubble, curing process: 120 DEG C/2h+180 DEG C/2h.As follows by thermogravimetric analysis (TGA) test performance after the solidification of this resin system: T
d5=355 DEG C, T
d10=375 DEG C, the quality retention rate at 400 DEG C is respectively 75.2%.Shock strength is 32.30KJm
-2.
Embodiment 2:
TDE-85, DDS, PCL-b-PDMS-b-PCL of taking are respectively 10g, 4g, 3g.By three kinds of components abundant hot melt mixing at 130 DEG C, in vacuum drying oven, place 24h remove bubble, curing process: 130 DEG C/2h+200 DEG C/2h.As follows by thermogravimetric analysis (TGA) test performance after the solidification of this resin system: T
d5=345 DEG C, T
d10=362 DEG C, the quality retention rate at 400 DEG C is respectively 67.3%.Shock strength is 35.67KJm
-2.
Embodiment 3:
TDE-85, DDS, PCL-b-PDMS-b-PCL of taking are respectively 10g, 5g, 5g.By three kinds of components abundant hot melt mixing at 130 DEG C, in vacuum drying oven, place 24h remove bubble, curing process: 140 DEG C/2h+220 DEG C/2h.As follows by thermogravimetric analysis (TGA) test performance after the solidification of this resin system: T
d5=327 DEG C, T
d10=341 DEG C, the quality retention rate at 400 DEG C is respectively 62.2%.Shock strength is 39.52KJm
-2.
Claims (5)
1. PCL-b-PDMS-b-PCL triblock copolymer modified epoxy and preparation method thereof, it is characterized in that the composition of raw materials of described modified system is by mass: epoxy resin is 100 parts (mass fractions), solidifying agent is 30 ~ 50 parts (mass fractions), and PCL-b-PDMS-b-PCL is 10 ~ 50 parts (mass fractions).
2. PCL-b-PDMS-b-PCL triblock copolymer modified epoxy according to claim 1 and preparation method thereof, it is characterized in that: the epoxy resin used is 4,5-oxepane-1,2-dioctyl phthalate 2-glycidyl ester (TDE-85), belong to cycloaliphatc glycidyl fat trifunctional epoxy resin, as shown in structural formula 1:
Structural formula 1TDE-85.
3. PCL-b-PDMS-b-PCL triblock copolymer modified epoxy according to claim 1 and preparation method thereof, is characterized in that: the solidifying agent used is amine curing agent: DDS (being called for short DDS), as shown in structural formula 2:
Structural formula 2DDS.
4. PCL-b-PDMS-b-PCL triblock copolymer modified epoxy according to claim 1 and preparation method thereof, is characterized in that: the PCL-b-PDMS-b-PCL triblock copolymer used is as shown in structural formula 3:
Structural formula 3PCL-b-PDMS-b-PCL.
5. PCL-b-PDMS-b-PCL triblock copolymer modified epoxy described in claim 1 ~ 4 and preparation method thereof, it is characterized in that preparation method is as follows: be cured after the TDE-85 of different mass proportioning, DDS and PCL-b-PDMS-b-PCL melt compounding is even.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510631505.2A CN105131531A (en) | 2015-09-29 | 2015-09-29 | Triblock copolymer modified epoxide resin and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510631505.2A CN105131531A (en) | 2015-09-29 | 2015-09-29 | Triblock copolymer modified epoxide resin and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105131531A true CN105131531A (en) | 2015-12-09 |
Family
ID=54717129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510631505.2A Pending CN105131531A (en) | 2015-09-29 | 2015-09-29 | Triblock copolymer modified epoxide resin and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105131531A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348792A (en) * | 2015-12-11 | 2016-02-24 | 安徽律正科技信息服务有限公司 | Anti-aging plasticizer for wood plastic composite material |
| CN107163204A (en) * | 2017-07-11 | 2017-09-15 | 四川大学 | A kind of preparation method and application of high-strength and high ductility thermosetting resin based composites |
| CN109135195A (en) * | 2018-08-27 | 2019-01-04 | 四川大学 | A method of high tenacity compound resin is prepared by the spontaneous nanostructure of constructing of block copolymer in epoxy matrix |
| CN109135194A (en) * | 2018-08-27 | 2019-01-04 | 四川大学 | A kind of microcosmic high-toughness epoxy resin composite material with polymer nanostructures |
| CN109251480A (en) * | 2018-08-27 | 2019-01-22 | 四川大学 | Block copolymer constructs and prepares the application of high-ductility composite material for particular nanostructure in epoxy resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106161A (en) * | 2006-10-26 | 2008-05-08 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
-
2015
- 2015-09-29 CN CN201510631505.2A patent/CN105131531A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106161A (en) * | 2006-10-26 | 2008-05-08 | Sumitomo Bakelite Co Ltd | Epoxy resin composition |
Non-Patent Citations (3)
| Title |
|---|
| L. KONCZOL, ET AL: ""Ultimate Properties of Epoxy Resins Modified with a Polysiloxane-Polycaprolactone Block Copolymer"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| ZHIGUANG XU, ET AL: ""Morphology and thermomechanical properties of nanostructured thermosetting blends of epoxy resin and poly(3-caprolactone)-block-polydimethylsiloxane-block-poly(3-caprolactone) triblock copolymer"", 《POLYMER》 * |
| 李慧琴等: ""PCL-b-PDMS-b-PCL 复合环氧树脂的表面结构"", 《物理化学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348792A (en) * | 2015-12-11 | 2016-02-24 | 安徽律正科技信息服务有限公司 | Anti-aging plasticizer for wood plastic composite material |
| CN107163204A (en) * | 2017-07-11 | 2017-09-15 | 四川大学 | A kind of preparation method and application of high-strength and high ductility thermosetting resin based composites |
| CN107163204B (en) * | 2017-07-11 | 2019-07-26 | 四川大学 | A kind of preparation method and application of high-strength and high ductility thermosetting resin based composites |
| CN109135195A (en) * | 2018-08-27 | 2019-01-04 | 四川大学 | A method of high tenacity compound resin is prepared by the spontaneous nanostructure of constructing of block copolymer in epoxy matrix |
| CN109135194A (en) * | 2018-08-27 | 2019-01-04 | 四川大学 | A kind of microcosmic high-toughness epoxy resin composite material with polymer nanostructures |
| CN109251480A (en) * | 2018-08-27 | 2019-01-22 | 四川大学 | Block copolymer constructs and prepares the application of high-ductility composite material for particular nanostructure in epoxy resin |
| CN109251480B (en) * | 2018-08-27 | 2022-03-04 | 四川大学 | Application of block copolymer in construction of specific nanostructure in epoxy resin and preparation of high-toughness composite material |
| CN109135194B (en) * | 2018-08-27 | 2023-11-24 | 四川大学 | Microcosmic high-toughness epoxy resin composite material with polymer nano structure |
| CN109135195B (en) * | 2018-08-27 | 2023-11-24 | 四川大学 | Method for preparing high-toughness composite resin through self-constructing nano structure of segmented copolymer in epoxy matrix |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105131531A (en) | Triblock copolymer modified epoxide resin and preparing method thereof | |
| CN102492116B (en) | Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method | |
| Gao et al. | High-performance conductive materials based on the selective location of carbon black in poly (ether ether ketone)/polyimide matrix | |
| CN108004779B (en) | Polyaryletherketone resin-based suspension sizing agent for carbon fibers and preparation method thereof | |
| CN102532809A (en) | Organosilicon-epoxy resin composition and preparation method thereof | |
| CN104448239A (en) | High-strength epoxy resin composite material and preparation method thereof | |
| CN105255438A (en) | Bisphenol a epoxy resin modified room temperature vulcanized silicone rubber and preparation method thereof | |
| CN112980372B (en) | Adhesive and preparation method thereof | |
| CN103146141A (en) | Low dielectric constant polyhedral oligomeric silsesquioxane (POSS)/ epoxy resin hybrid material and preparation method | |
| CN105368046B (en) | Cyanate ester resin/heat conduction filler composition, prepreg and its application | |
| CN105504713B (en) | A kind of 3D printing is material modified and preparation method thereof with polylactic acid microsphere | |
| CN101891957A (en) | Organic silicon resin-based heat-resisting wave-penetrating composite material and preparation method thereof | |
| Zhang et al. | Morphology and properties of TGDDM/DDS epoxy systems toughened by amino-bearing phenyl silicone resins | |
| CN103242793B (en) | Toughened single-component epoxy resin | |
| CN107286585A (en) | It is a kind of for epoxy PUR of high modulus carbon fiber prepreg and preparation method thereof | |
| CN104045978A (en) | Polyarylether nitrile/epoxy resin copolymerized modified composition and preparation method and application thereof | |
| CN104031355A (en) | Epoxy resin composition cured and modified by carboxyl-containing polyether nitrile sulphone ketone copolymer as well as preparation method and application of epoxy resin composition | |
| CN101885901A (en) | Biphenyl-structure-contained epoxy resin/montmorillonite nano composite material | |
| CN106700089B (en) | A kind of hybrid inorganic-organic core-shell particles and the preparation method and application thereof | |
| CN108976782A (en) | A kind of nylon composite materials and preparation method thereof modified based on hyperbranched epoxy resin | |
| CN101891936A (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN105694033B (en) | A kind of o-phthalonitrile resin composition and preparation method thereof and application method | |
| CN103665379B (en) | Nano-carbonate becomes the method for nucleosynthesis polyphenylene sulfide | |
| Chen et al. | Effect of Polyether Sulfone Resin on Micromorphology, Thermal, Mechanical, and Dielectric Properties of Epoxy–Bismaleimide Composite Material | |
| CN105331104A (en) | Modified thermosetting resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151209 |
|
| WD01 | Invention patent application deemed withdrawn after publication |