CN104131459A - CNTs-containing vinyl-ester carbon fiber sizing agent and preparation method thereof - Google Patents
CNTs-containing vinyl-ester carbon fiber sizing agent and preparation method thereof Download PDFInfo
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- CN104131459A CN104131459A CN201410373086.2A CN201410373086A CN104131459A CN 104131459 A CN104131459 A CN 104131459A CN 201410373086 A CN201410373086 A CN 201410373086A CN 104131459 A CN104131459 A CN 104131459A
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Abstract
The invention discloses a CNTs-containing vinyl-ester carbon fiber sizing agent and a preparation method thereof. The sizing agent is prepared from the following compositions: 0.5-2 wt% of a resin mixture, 0.1-1 wt% of aminated CNTs, and the balance acetone; and the resin mixture is obtained by mixing 10-20 parts by mass of vinyl resin, 0.1-0.5 part by mass of a radical initiator and 0.1-0.5 part by mass of a curing agent. The concrete preparation method comprises: weighing vinyl resin, the radical initiator and the curing agent according to the proportions, and mixing uniformly; weighing the resin mixture and aminated CNTs, adding acetone, and performing ultrasonic concussion processing under a sealing condition, so as to obtain the sizing agent. Aiming at the interface bonding problem between carbon fiber and MR13006 type unsaturated polyester, the amine functionalized carbon nanotube is introduced into the compound material interface through a sizing coating method, so that a protective layer on the fiber surface is formed and the interface bonding strength between fiber and matrix resin is improved, and the mechanical properties of the material are improved.
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 carbon fiber and strengthen unsaturated polyester composite.
Background technology
Research shows, vehicle complete vehicle weight decline 10%, and fuel efficiency can promote 6-8%, the every loss of weight 100kg of vehicle, every kilometer can be discharged the carbon dioxide of 5g less.Current auto industry is facing the double challenge of resources and environment, and automotive light weight technology is imperative.
The most representatively in advanced composite material to belong to carbon-fibre reinforced epoxy resin composite material, but because the price of epoxy resin is higher, and make longer hardening time the utilization ratio of mould reduce, increase production cost.Therefore, each large automobile production commercial city is at effort demand composite system cheaply.The MR13006 type resin of ASHLAND company, compare traditional epoxy resin and there is obvious price advantage, after being used in conjunction with suitable shrinking agent, can under comparatively wide in range raw material proportioning and condition of molding, produce the goods with A level surface, 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 can effectively reduce production costs, and 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, thereby affect the performance of the final performance of composite.The combination problem that solves the two interface just becomes the key issue that promotes material combination property.
Summary of the invention
The object of the invention is to solve carbon fiber with the poor problem of unsaturated polyester (UP) basal body interface binding ability, and vinyl ester sizing agent of a kind of amino-contained functionalization CNTs providing 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:
Taking 10～20g vinylite, 0.1～0.5g radical initiator and 0.1～0.5g curing agent mixes; Taking the aminated CNTs of 0.5～2g resin compound and 0.1～1g, to add acetone to solution quality be 100g, and under air-proof condition, 10～20min is processed in ultrasonic concussion, 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 the two keys in end can participate in unsaturated polyester (UP) matrix curing reaction (utilizing the radical reaction between two keys).Epoxide group can also occur with aminated CNTs in addition.
In the present invention, described radical initiator is TBPB, BPO etc., because TBPB is for 140 degrees Celsius of lower hot settings, can shorten hardening time, enhances productivity, and 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 carbon fiber with the interface of MR13006 type unsaturated polyester (UP) (production of Ashland company) in conjunction with problem; the method that CNT after functional amido is applied by starching is introduced composite material interface; be intended to when fiber surface forms protective layer improve fiber with the interface combination between matrix resin, improve the mechanical property of material.
Tool of the present invention has the following advantages:
One, aminated CNTs and M7270 type vinyl esters have good compatibility, and sizing agent can evenly apply at fiber surface;
Two, M7270 polyhydroxy molecular structure has improved it and has infiltrated at fiber surface, and the vinyl that chain is short and epoxy radicals, respectively with matrix resin and aminated CNTs effect, make the composite interlayer cutting performance after starching applies improve 34%.
Brief description of the drawings
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 variation of composite impact property 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 to this; every technical solution of the present invention is modified or is equal to replacement, 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 embodiment provides vinyl ester sizing agent of a kind of amino-contained functionalization CNTs and preparation method thereof, specifically completes according to the following steps:
One, the aminated processing of CNT
2g CNTs is placed in to 1000ml round-bottomed flask, the HNO that is carefully 69% by 380ml concentration
3, the H that 320ml concentration is 96%
2sO
4add flask and stir 1min with 30ml deionized water.Then ultrasonic processing 8h at 60 DEG C.After surface treatment completes sample through centrifugal wash away acid solution to pH be 7, after freeze drying, obtain carboxylated CNTs processing sample.In carboxylated CNTs, add 100mlSOCl
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 getting after above-mentioned chloride adds in ethylenediamine, reacts 48h at 80 DEG C, after suction filtration, cleans to neutral with distilled water, obtains aminated CNTs, obtains aminated CNTs product after freeze drying.
Two, contain the preparation of the vinyl ester sizing agent of CNTs:
Taking 15g RIPOXY M7270 type vinylite, 0.3g radical initiator TBPB and 0.3g1-methylimidazole mixes.Taking the aminated CNTs of 2g mixture and 1g, to add acetone to solution quality be 200g, and under air-proof condition, 15min is processed in ultrasonic concussion.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 be immersed in mass fraction and be in 5% ammonium bicarbonate soln, current density with 300mA/g is carried out anodized 4min to carbon fiber, oxidation finish a large amount of distilled water of rear use clean carbon fiber to pH be 7.After drying, carry out sizing agent coating processing with the prepared sizing agent of step 2.
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 the 4 SEM surface topography maps for fiber before and after starching.Dispersiveness through aminated CNTs-EDA after treatment in solvent-borne type sizing agent improves obviously, do not observe obvious agglomeration, the more untreated CNTs of CNTs quantity that is attached to fiber surface obviously increases, and CNTs presents and is uniformly distributed at fiber surface with different angles.These point of bulk density is moderate, and the different CNTs of dispersion angle can effectively improve fiber surface roughness, thereby fortifying fibre surface is with the mechanical locking action between unsaturated polyester (UP) matrix.After M7270-CNTs-EDA surface applies, groove pattern still exists, but part groove 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 between pipe tangle very favourable.On the other hand, the change of functionalization to CNTs outer wall construction and the introducing of organic group effectively raise the dispersiveness of CNTs in organic solution.
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 of comparing not starching processing and has been improved 30%.New Sizing agent effectively raises fiber with the interface combination 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 prepared composite of untreated fiber, obvious Interface Cracking is occurring after failure by shear, fiber more easily moves in matrix, and many fibers are pulled out matrix under the effect of stress.Observation is pulled out fiber surface and can finds, it is smooth clean and tidy that fiber is drawn out part, have no any resin adhesion, from the judgement of pull-out length, fiber has experienced the slip of long distance, and part fiber departs from matrix resin completely, form geometry with radially consistent hole, interface of fiber at resin surface, and sidewall is smooth.These phenomenons all illustrate untreatment fiber with the interface between unsaturated polyester (UP) in conjunction with poor.Port pattern after starching is compared with the shearing area pattern of untreated carbon fiber, interface is in conjunction with increasing, Interface Cracking phenomenon reduces to some extent, fiber is still less drawn out under external force, and pull-out distance reduces to some extent, and part pulls out fiber surface uniform resin bed adhesion, and the rupture cross section pattern of resin is no longer smooth just like that as untreatment fiber, there are a large amount of broken resin mass, in the process that above phenomenon explanation fiber is extracted under external force from matrix, run into larger resistance.
Fig. 8 is the variation of composite impact property before and after starching.As can be seen from the figure, CNTs introduces the crack expansion power that has greatly improved composite, and this explanation has effectively absorbed ability in crack propagation process at CNTs, the fracture toughness of material is strengthened.
Table 1 is contact angle and the surface energy variation of fiber before and after starching in polarity and non-polar solven, and the contact angle of starching naked fiber in deionized water and diiodomethane is not respectively 73.2 and 46.8 °, and polarity and the nonpolar component of surface energy 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 explanation sizing agent effectively improves the polarity of fiber surface, but not the raising of polar component introduces by CNTs the roughened surface that structure is selected.The increase of fiber surface polarity is conducive to improve the compatibility of fiber with resin, and the increase of roughness is conducive to improve the mechanical locking action of fiber with resin.
The contact angle of table 1 carbon fiber and surperficial energy
Detailed description of the invention two: what present embodiment was different from detailed description of the invention one is, 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.
Detailed description of the invention three: what present embodiment was different from detailed description of the invention one is, 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.
Detailed description of the invention four: what present embodiment was different from detailed description of the invention one is, 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.
Claims (9)
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.
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. according to the vinyl ester carbon fiber sizing agent containing CNTs described in claim 1,2,3,4 or 5, it is characterized in that described vinylite is M7270 vinylite.
7. according to the vinyl ester carbon fiber sizing agent containing CNTs described in claim 1,2,3,4 or 5, it is characterized in that described radical initiator is TBPB or BPO.
8. according to the vinyl ester carbon fiber sizing agent containing CNTs described in claim 1,2,3,4 or 5, it is characterized in that described curing agent is imidazole curing agent used for epoxy resin.
9. a preparation method for the vinyl ester sizing agent of amino-contained functionalization CNTs, specifically completes according to the following steps:
Taking 10～20g vinylite, 0.1～0.5g radical initiator and 0.1～0.5g curing agent mixes; Taking the aminated CNTs of 0.5～2g resin compound and 0.1～1g, to add acetone to solution quality be 100g, and under air-proof condition, 10～20min is processed in ultrasonic concussion, obtains the vinyl ester sizing agent of amino-contained functionalization CNTs.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633741A (en) * | 2016-12-29 | 2017-05-10 | 哈尔滨工业大学 | Interfacial modification method of carbon fibers/unsaturated resin |
| CN108752943A (en) * | 2018-05-24 | 2018-11-06 | 昆明理工大学 | A kind of preparation method of epoxy resin-matrix ambroin |
| 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 |
| 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 |
Citations (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 |
| CN101718037A (en) * | 2009-12-10 | 2010-06-02 | 哈尔滨工业大学 | Preparation method of root-like carbon nanotube grafting carbon fiber reinforcement |
| CN101736593A (en) * | 2010-01-08 | 2010-06-16 | 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 |
| CN102627993A (en) * | 2012-03-20 | 2012-08-08 | 哈尔滨工业大学 | Preparation method of water-soluble graphene oxide-carbon nanotube extreme-pressure lubrication additive |
| US8398950B2 (en) * | 2002-11-18 | 2013-03-19 | William Marsh Rice University | Condensation polymers having covalently bound carbon nanotubes |
-
2014
- 2014-07-31 CN CN201410373086.2A patent/CN104131459B/en active Active
Patent Citations (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 |
| US8398950B2 (en) * | 2002-11-18 | 2013-03-19 | William Marsh Rice University | Condensation polymers having covalently bound carbon nanotubes |
| CN101718037A (en) * | 2009-12-10 | 2010-06-02 | 哈尔滨工业大学 | Preparation method of root-like carbon nanotube grafting carbon fiber reinforcement |
| CN101736593A (en) * | 2010-01-08 | 2010-06-16 | 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 |
| CN102627993A (en) * | 2012-03-20 | 2012-08-08 | 哈尔滨工业大学 | Preparation method of water-soluble graphene oxide-carbon nanotube extreme-pressure lubrication additive |
Non-Patent Citations (1)
| Title |
|---|
| WU ZIJIAN ET AL.: "Interface enhancement of carbon fiber reinforced unsaturated polyester composites with sizing agent containing carbon nanotubes", 《JOURNAL OF REINFORCED PLASTICS AND COMPOSITES》, 8 October 2013 (2013-10-08), pages 1 - 10 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633741A (en) * | 2016-12-29 | 2017-05-10 | 哈尔滨工业大学 | Interfacial modification method of carbon fibers/unsaturated resin |
| 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 |
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