CN104131459B - A kind of vinyl ester carbon fiber sizing agent containing CNTs and preparation method thereof - Google Patents
A kind of vinyl ester carbon fiber sizing agent containing CNTs and preparation method thereof Download PDFInfo
- Publication number
- CN104131459B CN104131459B CN201410373086.2A CN201410373086A CN104131459B CN 104131459 B CN104131459 B CN 104131459B CN 201410373086 A CN201410373086 A CN 201410373086A CN 104131459 B CN104131459 B CN 104131459B
- Authority
- CN
- China
- Prior art keywords
- sizing agent
- vinylite
- resin compound
- cnts
- aminated
- 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
Abstract
The invention discloses a kind of vinyl ester carbon fiber sizing agent containing CNTs and preparation method thereof.Described sizing agent is prepared from by following composition: resin compound 0.5 ~ 2wt.%, aminated CNTs0.1 ~ 1wt.%, acetone: surplus, wherein: resin compound is mixed by vinylite 10 ~ 20, radical initiator 0.1 ~ 0.5 and curing agent 0.1 ~ 0.5 according to mass ratio, and concrete preparation method is: take vinylite, radical initiator and curing agent by proportioning and mix; Take resin compound and aminated CNTs adds acetone, under air-proof condition, ultrasonic vibration process, obtains sizing agent.The present invention is directed to the interface cohesion problem of carbon fiber with MR13006 type unsaturated polyester (UP); the method that CNT after functional amido is applied by starching is introduced composite material interface; be intended to improve fiber with the interface cohesion between matrix resin while fiber surface forms protective layer, improve the mechanical property of material.
Description
Technical field
The present invention relates to a kind of sizing agent and preparation method thereof, be specifically related to a kind of vinyl ester carbon fiber sizing agent containing CNTs and preparation method thereof, be adapted to fibre reinforced unsaturated polyester composite.
Background technology
Research shows, vehicle complete vehicle weight declines 10%, and fuel efficiency can promote 6-8%, the every loss of weight 100kg of vehicle, every kilometer of carbon dioxide that can discharge 5g less.Current auto industry is facing the double challenge of resources and environment, and automotive light weight technology is imperative.
In advanced composite material, most is representational will belong to carbon-fibre reinforced epoxy resin composite material, but due to the price of epoxy resin higher, and make longer hardening time the utilization ratio of mould reduce, add production cost.Therefore, each large automobile production commercial city is at the composite system of the demand of effort low cost.The MR13006 type resin of ASHLAND company, compare traditional epoxy resin and there is obvious price advantage, when with suitable shrinking agent with the use of after can produce the goods with A level surface under comparatively wide in range pulp furnish and condition of molding, not only can compression molding but also can injection moulding.Be applicable to very much preparation SMC, TMC and BMC goods.Its quick-setting characteristic effectively can reduce production cost, enhances productivity.Above advantage makes this curing system be well suited for business compression molding.But the random graphits structure of carbon fiber surface makes fiber surface present chemical inertness, poor with the unsaturated polyester (UP) interface compatibility of polarity, affect bonding interface, thus affect the performance of the final performance of composite.Just the key issue becoming lifting material combination property in conjunction with problem at both solutions interface.
Summary of the invention
The object of the invention is to solve the problem of carbon fiber with unsaturated polyester (UP) basal body interface binding ability difference, and vinyl ester sizing agent of a kind of amino-contained functionalization CNTs provided and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
The vinyl ester sizing agent of a kind of amino-contained functionalization CNTs, be prepared from by following composition: resin compound 0.5 ~ 2wt.%, aminated CNTs0.1 ~ 1wt.%, acetone: surplus, described resin compound is mixed by vinylite 10 ~ 20, radical initiator 0.1 ~ 0.5 and curing agent 0.1 ~ 0.5 according to mass ratio.
A preparation method for the vinyl ester sizing agent of amino-contained functionalization CNTs, specifically completes according to the following steps:
Take 10 ~ 20g vinylite, 0.1 ~ 0.5g radical initiator and 0.1 ~ 0.5g curing agent to mix; Taking 0.5 ~ 2g resin compound and the aminated CNTs of 0.1 ~ 1g, to add acetone to solution quality be 100g, and ultrasonic vibration process 10 ~ 20min under air-proof condition, obtains the vinyl ester sizing agent of amino-contained functionalization CNTs.
In the present invention, vinylite is M7270 vinylite.M7270 is one end epoxide group, a terminal double bond, and side chain has the vinylite of great amount of hydroxy group, and its molecular formula is as follows:
The advantage that it compares traditional epoxy resin sizing agent is that end double bond can participate in unsaturated polyester (UP) matrix curing reaction (utilizing the radical reaction between double bond).Epoxide group can also occur with aminated CNTs in addition.
In the present invention, described radical initiator is TBPB, BPO etc., and because TBPB is used for 140 degrees Celsius of lower hot settings, can shorten hardening time, enhance productivity, therefore radical initiator of the present invention is preferred TBPB.
In the present invention, described curing agent is imidazole curing agent used for epoxy resin.
The present invention is directed to the interface cohesion problem of carbon fiber with MR13006 type unsaturated polyester (UP) (production of Ashland company); the method that CNT after functional amido is applied by starching is introduced composite material interface; be intended to improve fiber with the interface cohesion between matrix resin while fiber surface forms protective layer, improve the mechanical property of material.
Tool of the present invention has the following advantages:
One, aminated CNTs and M7270 type vinyl esters has good compatibility, and sizing agent evenly can apply at fiber surface;
Two, M7270 polyhydroxy molecular structure improves it and infiltrates at fiber surface, and the vinyl that chain is short and epoxy radicals are respectively with matrix resin and aminated CNTs effect, and the composite interlayer cutting performance after starching is applied improves 34%.
Accompanying drawing explanation
Fig. 1 is the SEM photo of aminated front CNTs;
Fig. 2 is the SEM photo of aminated rear CNTs;
Fig. 3 is the SEM surface topography map of fiber before starching;
Fig. 4 is the SEM surface topography map of fiber after starching;
Fig. 5 is the interlaminar shear strength of composite before and after fiber starching;
Fig. 6 is the shear fracture pattern of composite before starching;
Fig. 7 is the shear fracture pattern of composite after starching;
Fig. 8 is the change of composite impact performance before and after starching.
Detailed description of the invention
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Detailed description of the invention one: present embodiments provide for vinyl ester sizing agent of a kind of amino-contained functionalization CNTs and preparation method thereof, specifically complete according to the following steps:
One, the aminated process of CNT
2gCNTs being placed in 1000ml round-bottomed flask, is carefully the HNO of 69% by 380ml concentration
3, 320ml concentration is the H of 96%
2sO
4add flask with 30ml deionized water and stir 1min.Then ultrasonic process 8h at 60 DEG C.After surface treatment completes, to wash away acid solution to pH be 7 to sample through centrifugal, obtains carboxylated CNTs processing sample after freeze drying.100mlSOCl is added in carboxylated CNTs
2with the mixed liquor of DMF, be heated to 76 DEG C, back flow reaction 72h, unnecessary SOCl is gone out in decompression distillation
2.The CNTs got after above-mentioned chloride adds in ethylenediamine, reacts 48h at 80 DEG C, extremely neutral with distilled water cleaning after suction filtration, obtains aminated CNTs, obtains aminated CNTs product after freeze drying.
Two, containing the preparation of the vinyl ester sizing agent of CNTs:
Take 15gRIPOXYM7270 type vinylite, 0.3g radical initiator TBPB and 0.3g1-methylimidazole to mix.Taking 2g mixture and the aminated CNTs of 1g, to add acetone to solution quality be 200g, ultrasonic vibration process 15min under air-proof condition.Preparing content of carbon nanotubes is 1wt% sizing agent, seals for subsequent use.
Three, the anodized of carbon fiber: carbon fiber synnema is wrapped on rectangle glass framework, then being immersed in mass fraction is in the ammonium bicarbonate soln of 5%, carry out anodized 4min with the current density of 300mA/g to carbon fiber, it is 7 to pH that oxidation terminates rear use a large amount of distilled water cleaning carbon fiber.The sizing agent of drying prepared by rear step 2 carries out sizing agent coating processing.
Fig. 1 and 2 is the SEM photo of aminated CNTs, and the CNTs after as can be seen from the figure aminated has better dissolubility and dispersiveness.
Fig. 3 and 4 is the SEM surface topography map of fiber before and after starching.The dispersiveness of CNTs-EDA after aminated process in solvent-borne type sizing agent improves obviously, do not observe obvious agglomeration, the more untreated CNTs of CNTs quantity being attached to fiber surface obviously increases, and CNTs to present at fiber surface with different angles and is uniformly distributed.These tamped density are moderate, and the different CNTs of dispersion angle can effectively improve fiber surface roughness, thus fortifying fibre surface is with the mechanical locking action between unsaturated polyester (UP) matrix.After the coating of M7270-CNTs-EDA surface, groove pattern still exists, but part of trench is owing to being reduced by resin overburden depth.As can be seen from the figure, CNTs is truncated to several microns of even hundreds of Nano grades by oxidation processes, the minimizing of length for open tangle between pipe very favourable.On the other hand, functionalization effectively raises the dispersiveness of CNTs in organic solution to the change of CNTs outer wall construction and the introducing of organic group.
Fig. 5 is the interlaminar shear strength of composite before and after starching.As we can see from the figure, the composite interlayer after starching is sheared the composite material strength comparing non-starching process and is improve 30%.New Sizing agent effectively raises fiber with the interface cohesion between matrix resin.
Fig. 6 and 7 is Laminated Shear Deformable destruction fracture apperance before and after starching.As can be seen from the figure, by the composite prepared by untreated fiber, there occurs obvious Interface Cracking after failure by shear, fiber more easily moves in the base, and many fibers are pulled out matrix under the effect of stress.Observation is pulled out fiber surface and can finds, it is clean and tidy that fiber is drawn out portion smooth, have no any resin adhesion, judge from pull-out length, fiber experienced by the slip of long distance, and few fibers departs from matrix resin completely, form geometry with consistent hole, the radial interface of fiber at resin surface, and sidewall is smooth.These phenomenons all illustrate that untreatment fiber is poor with the interface cohesion between unsaturated polyester (UP).Port pattern after starching is compared with the shearing area pattern of untreated carbon fiber, interface cohesion increases, Interface Cracking phenomenon reduces to some extent, less fiber is drawn out under external force, and pull-out distance reduces to some extent, part pull-out fiber surface has uniform resin bed adhesion, and the rupture cross section pattern of resin is no longer smooth just like that as untreatment fiber, occur a large amount of broken resin mass, above phenomenon illustrates in the process that fiber is extracted under external force from matrix and runs into larger resistance.
Fig. 8 is the change of composite impact performance before and after starching.As can be seen from the figure, CNTs introduces the crack expansion power greatly improving composite, and this explanation effectively absorbs ability at CNTs in crack propagation process, and the fracture toughness of material is strengthened.
Table 1 is the contact angle of fiber before and after starching in polarity and non-polar solven and surface energy variation, and the contact angle of non-starching naked fiber in deionized water and diiodomethane is respectively 73.2 and 46.8 °, and the polarity of surface energy and non-polar components are all relatively low.After starching, the contact angle of fiber in water and diiodomethane is respectively 59.1 and 19.2 °, compare unsized fiber, its polar component and dispersive component are significantly increased, this illustrates that sizing agent effectively improves the polarity of fiber surface, and the raising of non-polar components then introduces by CNTs the roughened surface that structure selects.The increase of fiber surface polarity is conducive to improving the compatibility of fiber with resin, and the increase of roughness is then conducive to improving the mechanical locking action of fiber with resin.
The contact angle of table 1 carbon fiber and surface energy
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike, described sizing agent is prepared from by following composition: resin compound 0.7wt.%, aminated CNTs0.2wt.%, acetone: surplus, and described resin compound is mixed by vinylite 12, radical initiator 0.2 and curing agent 0.2 according to mass ratio.
Detailed description of the invention three: present embodiment and detailed description of the invention one unlike, described sizing agent is prepared from by following composition: resin compound 1.4wt.%, aminated CNTs0.7wt.%, acetone: surplus, and described resin compound is mixed by vinylite 14, radical initiator 0.4 and curing agent 0.4 according to mass ratio.
Detailed description of the invention four: present embodiment and detailed description of the invention one unlike, described sizing agent is prepared from by following composition: resin compound 1.8wt.%, aminated CNTs0.9wt.%, acetone: surplus, and described resin compound is mixed by vinylite 18, radical initiator 0.5 and curing agent 0.5 according to mass ratio.
Claims (6)
1. the vinyl ester carbon fiber sizing agent containing CNTs, it is characterized in that described sizing agent is prepared from by following composition: resin compound 0.5 ~ 2wt.%, aminated CNTs0.1 ~ 1wt.%, acetone: surplus, wherein: resin compound is mixed by vinylite 10 ~ 20, radical initiator 0.1 ~ 0.5 and curing agent 0.1 ~ 0.5 according to mass ratio, described vinylite is M7270 vinylite, radical initiator is TBPB or BPO, and curing agent is imidazole curing agent used for epoxy resin.
2. the vinyl ester carbon fiber sizing agent containing CNTs according to claim 1, it is characterized in that described sizing agent is prepared from by following composition: resin compound 1wt.%, aminated CNTs0.5wt.%, acetone: surplus, described resin compound is mixed by vinylite 15, radical initiator 0.3 and curing agent 0.3 according to mass ratio.
3. the vinyl ester carbon fiber sizing agent containing CNTs according to claim 1, it is characterized in that described sizing agent is prepared from by following composition: resin compound 0.7wt.%, aminated CNTs0.2wt.%, acetone: surplus, described resin compound is mixed by vinylite 12, radical initiator 0.2 and curing agent 0.2 according to mass ratio.
4. the vinyl ester carbon fiber sizing agent containing CNTs according to claim 1, it is characterized in that described sizing agent is prepared from by following composition: resin compound 1.4wt.%, aminated CNTs0.7wt.%, acetone: surplus, described resin compound is mixed by vinylite 14, radical initiator 0.4 and curing agent 0.4 according to mass ratio.
5. the vinyl ester carbon fiber sizing agent containing CNTs according to claim 1, it is characterized in that described sizing agent is prepared from by following composition: resin compound 1.8wt.%, aminated CNTs0.9wt.%, acetone: surplus, described resin compound is mixed by vinylite 18, radical initiator 0.5 and curing agent 0.5 according to mass ratio.
6. a preparation method for the vinyl ester sizing agent of amino-contained functionalization CNTs, specifically completes according to the following steps:
Take 10 ~ 20g vinylite, 0.1 ~ 0.5g radical initiator and 0.1 ~ 0.5g curing agent to mix, described vinylite is M7270 vinylite, and radical initiator is TBPB or BPO, and curing agent is imidazole curing agent used for epoxy resin; Taking 0.5 ~ 2g resin compound and the aminated CNTs of 0.1 ~ 1g, to add acetone to solution quality be 100g, and ultrasonic vibration process 10 ~ 20min under air-proof condition, obtains the vinyl ester sizing agent of amino-contained functionalization CNTs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410373086.2A CN104131459B (en) | 2014-07-31 | 2014-07-31 | A kind of vinyl ester carbon fiber sizing agent containing CNTs and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410373086.2A CN104131459B (en) | 2014-07-31 | 2014-07-31 | A kind of vinyl ester carbon fiber sizing agent containing CNTs and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104131459A CN104131459A (en) | 2014-11-05 |
| CN104131459B true CN104131459B (en) | 2016-03-16 |
Family
ID=51804301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410373086.2A Active CN104131459B (en) | 2014-07-31 | 2014-07-31 | A kind of vinyl ester carbon fiber sizing agent containing CNTs and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104131459B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633741B (en) * | 2016-12-29 | 2018-07-03 | 哈尔滨工业大学 | A kind of interface modification method of carbon fiber/unsaturated-resin |
| CN109837740A (en) * | 2017-11-27 | 2019-06-04 | 四川东邦碳纤维材料有限公司 | A kind of surface treatment method of carbon fiber and the carbon fiber of preparation |
| CN108752943A (en) * | 2018-05-24 | 2018-11-06 | 昆明理工大学 | A kind of preparation method of epoxy resin-matrix ambroin |
| CN110655770A (en) * | 2018-06-29 | 2020-01-07 | 合肥杰事杰新材料股份有限公司 | High-performance carbon fiber reinforced resin and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03185181A (en) * | 1989-12-12 | 1991-08-13 | Idemitsu Kosan Co Ltd | Method for treating surface of carbon fiber |
| US7452519B2 (en) * | 2002-11-18 | 2008-11-18 | William Marsh Rice University | Sidewall functionalization of single-wall carbon nanotubes through C-N bond forming substitutions of fluoronanotubes |
| CN101718037B (en) * | 2009-12-10 | 2012-03-28 | 哈尔滨工业大学 | Preparation method of root-like carbon nanotube grafting carbon fiber reinforcement |
| CN101736593B (en) * | 2010-01-08 | 2011-11-30 | 哈尔滨工业大学 | Preparation method of water-base epoxy resin sizing agent for carbon fiber |
| CN102276795A (en) * | 2011-06-22 | 2011-12-14 | 同济大学 | Preparation method of glass fiber/carbon nanotube/epoxy resin multi-dimensional hybrid composite material |
| CN102627993B (en) * | 2012-03-20 | 2013-06-05 | 哈尔滨工业大学 | Preparation method of water-soluble graphene oxide-carbon nanotube extreme-pressure lubrication additive |
-
2014
- 2014-07-31 CN CN201410373086.2A patent/CN104131459B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104131459A (en) | 2014-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104131459B (en) | A kind of vinyl ester carbon fiber sizing agent containing CNTs and preparation method thereof | |
| CN105802142A (en) | Graphene modified fiber reinforced resin-based composite material and preparation method thereof | |
| CN103665769B (en) | The preparation method of the multiple dimensioned fiber prepreg material of nano-micrometre | |
| CN101100079B (en) | Core-shell type multifunctional composite wood precursor solution and its preparation method | |
| CN104387671B (en) | A kind of preparation method of PA6/PP/ CNT High performance nanometer composite material | |
| CN108035143B (en) | Method for simultaneously improving interface strength and toughness of carbon fiber epoxy composite material | |
| CN104497360A (en) | Nano-silica immobilized hindered phenol antioxidant as well as preparation method and application of antioxidant | |
| CN103570255A (en) | Glass fiber infiltrating agent composition as well as preparation method and application thereof | |
| CN102924910B (en) | Method of preparing high-performance glass-fiber reinforced polyamide conductive composite | |
| CN107629224A (en) | The preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites | |
| CN103865295A (en) | Method for polymer surface modification of hollow glass micro-bead | |
| CN109135187B (en) | Preparation method of hybrid particle toughened epoxy resin composite material | |
| CN107382180A (en) | A kind of high ductility enhanced water resistance cement-base composite material of high intensity and preparation method thereof | |
| CN103525006B (en) | A kind of nanometer SiO2The preparation method of modified glass-fiber/epoxy resin composite material | |
| CN109306150A (en) | A kind of preparation method of room temperature curing epoxy composite material | |
| CN104131455B (en) | A kind of preparation method of the preliminary treatment aramid fiber short fibre for rubber | |
| CN108192286A (en) | Composite insulator and preparation method thereof | |
| CN108504041A (en) | A kind of epoxy resin/poly ion liquid composite material and preparation method | |
| CN106835326B (en) | High-performance graphene composite polyvinyl alcohol fiber and preparation method and application thereof | |
| Liu et al. | Study on wood chips modification and its application in wood-cement composites | |
| He et al. | A facile way to modify carbon fibers and its effect on mechanical properties of epoxy composites | |
| KR20040058540A (en) | Composition of mortar that is mixed suface modified fiber for repair and renovation of concrete structures and its manufacturing process | |
| CN101445646A (en) | Preparation method of polymeric based carbon nano tube composite material in the technical field of nano-materials | |
| CN106380607A (en) | Preparation method of modified wood powder | |
| CN103897345B (en) | TiO 2the preparation method of/PU-EP matrix material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |