CN101649553B - Method for preparing PBO fibre composite material and special surface treating agent thereof - Google Patents
Method for preparing PBO fibre composite material and special surface treating agent thereof Download PDFInfo
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- CN101649553B CN101649553B CN2009100240057A CN200910024005A CN101649553B CN 101649553 B CN101649553 B CN 101649553B CN 2009100240057 A CN2009100240057 A CN 2009100240057A CN 200910024005 A CN200910024005 A CN 200910024005A CN 101649553 B CN101649553 B CN 101649553B
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Abstract
The invention discloses a special surface treating agent for PBO fibre, which is characterized by comprising 15-30% of terminal carboxyl group-containing liquid rubber with the molecular weight of 2500-3500 and 70-85% of solvent acetone according to the mass percent. The invention also discloses a method for preparing a composite material by the PBO fibre processed by the special surface treatingagent. The method comprises the following steps: immersing the PBO fibre into a container provided with the special surface treating agent, immersing the processed PBO fibre into homogeneous phase basal body glue liquid, then winding PBO fibre bundles on an NOL ring mould and solidifying at room temperature; then, putting into a vacuum drying oven, heating, solidifying, cooling naturally to the room temperature, demolding to obtain a PBO fibre reinforcement composite material. The shearing strength value of the composite material prepared by the PBO fibre processed by adopting the special surface treating agent is enhanced from 12-25MPa of the prior art to 26.28-29.32MPa.
Description
Technical field
The present invention relates to a kind of preparation method of composite, particularly the preparation method of BPO fibrous composite.Also relate to a kind of surface conditioning agent, particularly BPO fiber special surface treating agent.
Background technology
Document " number of patent application is 200310107679.6 Chinese patent " discloses the pbo fiber surface modifying treatment of a kind of polymer matrix composite with enhancing.This method is immersed in pbo fiber in the plastics or glass container that the grafting liquid solution is housed.With said vesse sealing and use gamma-ray irradiation, placement was taken out pbo fiber after 20 hours to 30 hours from container after irradiation was finished then.This method is carried out mutual radiation with fiber base material with the grafting liquid solution under situation about directly contacting, thereby graft copolymerization takes place.Because graft reaction only occurs on the cortex of fiber, the orientation texture of the pbo fiber strand sound of not can't stand any longer, the mechanical property of fiber reduces less.But this method operating process not only needs special high-energy ray radiation appliance, and the processing time is longer, is not easy to continuous operation.
And the resin system of design of the resin system prescription in the document and the prepared pbo fiber reinforced composite of performance study thereof, the shear strength value of its composite is 12～25MPa.
Therefore, develop new pbo fiber surface treatment method, make fiber surface produce easily the functional group who combines with matrix generation chemical bond such as epoxy resin, guarantee that promptly the engineering properties after fiber and the resin compounded strengthens, the various performances that yet guarantee the fiber cross section direction are not suffered a loss, and are present research emphasis.Method and prescription thereof with finishing agent processing pbo fiber surface of the present invention can overcome the deficiencies in the prior art, and the pbo fiber after handling through finishing agent can make the surface nature of pbo fiber take place than obvious variation.
Common the having of resin matrix of preparation pbo fiber reinforced composite in the bibliographical information: the homemade epoxy-resin systems of researcher, epoxy resin TDE-85 system, the system of according to a certain ratio TDE-85 EP and E-51 EP being mixed, epoxy resin E-51 system.The curing agent that is adopted has: modified amine curing agent, anhydride curing agent etc.In patent documentation, not seeing has and the report of pbo fiber coupling with the resin matrix system.From the result of study of open source literature as seen, the prepared composite shear strength of these resin systems remains further to be improved.Be the composite of preparation high shear strength, need invention and the epoxy-resin systems of handling back pbo fiber coupling, to obtain the polymer matrix composites of high shear strength.The polymer matrix composites of high shear strength are the advanced configuration materials that has application potential in the Aeronautics and Astronautics field.
Summary of the invention
In order to overcome the low deficiency of pbo fiber reinforced composite shear strength of art methods preparation, the invention provides a kind of preparation method of BPO fibrous composite, after pbo fiber handled with special treating agent, through matrix glue impregnation of the present invention, prepare the pbo fiber reinforced composite, can obtain the polymer matrix composites of high shear strength.
The technical solution adopted for the present invention to solve the technical problems: a kind of BPO fiber special surface treating agent is characterized in: contain mass percent and be 15～30%, molecular weight be 2500～3500 contain end carboxyl liquid rubber and mass percent is 70～85% solvent acetone.
Described liquid rubber be CTPB, CTPB-styrene or CTPB-acrylonitrile any.
A kind of method that adopts the BPO fiber production composite of above-mentioned special surface treating agent processing is characterized in comprising the steps:
(a) according to mass percent be 15～30%, molecular weight be 2500～3500 contain end carboxyl liquid rubber and mass percent is that 70～85% solvent acetone are mixed with surface conditioning agent;
(b) immersion time 8～15s is equipped with in the container of surface conditioning agent in the pbo fiber immersion;
(c) according to the epoxy resin of 100 parts by mass, add curing agent 27～32 parts by mass, adding makes the epoxy resin mass percent account for 13～16% solvent acetone, and each component mixed dissolution becomes homogeneous phase matrix glue;
(d) will immerse 6～15s in the homogeneous phase matrix glue through the pbo fiber after step (b) processing, then the pbo fiber wrapping be encircled on the mould around NOL, and place 24～30h under the room temperature and solidify;
(e) put into vacuum drying chamber again and be heating and curing, condition is heating and curing: vacuum-0.1～-0.3MPa, under 70 ℃ of conditions, be incubated 2h then, under 120 ℃ of conditions, be incubated 2h, behind insulation 5h under 180 ℃ of conditions, naturally cool to room temperature, the demoulding promptly gets the pbo fiber reinforced composite.
Described epoxy resin be contain in the molecule epoxide number be 0.41～0.80 epoxy resin any or appoint several.
Described curing agent be diaminodiphenyl ether, m-phenylene diamine (MPD) or diamino-diphenyl sulfone any.
The invention has the beneficial effects as follows:
The advantage of pbo fiber special treating agent of the present invention mainly is: 1. the processing time is short; 2. do not need special device.After fiber was handled through special surface treating agent, significant change had taken place in the component ratio of pbo fiber chemical element, is mainly reflected in C, N, three kinds of elements of O, O/C, N/C atom content are than variation has all obviously taken place, the O/C ratio is significantly improved, and the N constituent content reduces, and N/C is than obviously descending.After showing treated dose of modification of pbo fiber, polar group has been introduced on its surface, has increased surperficial polarity part.The O/C ratio increases, and the O that is increased can form active function groups, and these surperficial activity chemistry components can be reacted with curing agent again with the epoxy resin reaction, thereby make the chemical bond that produces linkage interface between fiber and the resin when fiber and resin compounded.
Pbo fiber after handling through pretreating reagent is carried out the diffuse reflectance IR test, and the variation of fiber surface chemical composition the results are shown in accompanying drawing before and after handling with research.
Contain in the structure of finishing agent polarity-the COOH group, having must reactivity.Infrared waves spectrogram before and after handle through finishing agent on contrast pbo fiber surface, as can be seen: at 2400cm
-1The wave number place, significant change has taken place in the power relatively of absworption peak, and this peak is-characteristic absorption peak of COOH group.Show that finishing agent successfully has been coated in the pbo fiber surface, and then played the effect that changes pbo fiber surface infiltration performance.
Adopt its shear strength value of the prepared pbo fiber reinforced composite of epoxy-resin systems of the present invention to bring up to 26.28～29.32MPa by 12～25MPa of prior art.
Below in conjunction with the drawings and specific embodiments the present invention is elaborated.
Description of drawings
Accompanying drawing is pbo fiber and the untreated pbo fiber diffuse reflectance IR figure that handles through special surface treating agent.
The specific embodiment
Embodiment 1: with pbo fiber immerse by mass percent be 15%, molecular weight formed in the finishing agent by 2500～3500 CTPB (CTPB) and solvent acetone, the immersion time is 8s, takes out pbo fiber after finishing from container.
Preparation is by the epoxy resin E-44 of 100 parts by mass, the DDE of 27 parts by mass, and the consumption of solvent acetone is the 15% matrix glue of determining by epoxy resin mass percent in the glue, then the matrix glue is poured in the steeping vat.Make the pbo fiber of 68 parts by mass immerse above-mentioned matrix glue, the immersion time is 8s, then Wrapping formed on NOL ring mould, place 24h under the room temperature, then sample is put into vacuum drying chamber and is cured, in vacuum be-the 0.1MPa condition under, the curing process of pbo fiber composite is: 70 ℃ of following heating 2h, be warming up to 120 ℃ of heating 2h, continue to be warming up to 180 ℃ of heating 5h.Close drying box after solidifying end, naturally cool to room temperature, the demoulding promptly gets pbo fiber and strengthens polymer matrix composites.
The polymer-matrix pbo fiber reinforced composite NOL ring sample that obtains carries out the interlayer shear performance test according to GB/T3357-82, and its shear strength value is 29.32MPa.
Embodiment 2: with pbo fiber immerse by mass percent be 15%, molecular weight formed in the finishing agent by 2500～3500 CTPB-acrylonitrile (CTBN) and solvent acetone, the immersion time is 6s, takes out pbo fiber after finishing from container.Preparation is by the epoxy resin E-44 of 100 parts by mass, the DDS of 30 parts by mass, and the consumption of solvent acetone is the 16% matrix glue of determining by epoxy resin mass percent in the glue, then the matrix glue is poured in the steeping vat.Making the pbo fiber of 70 parts by mass immerse the above-mentioned matrix glue immersion time is 10s, Wrapping formed on NOL ring mould, place 24h under the room temperature, then sample being put into vacuum drying chamber is cured, in vacuum be-the 0.1MPa condition under, the curing process of pbo fiber composite is: 70 ℃ are heated 2h down, are warming up to 120 ℃ of heating 2h, continue to be warming up to 180 ℃ of heating 5h.Close drying box after solidifying end, naturally cool to room temperature, the demoulding promptly gets pbo fiber and strengthens polymer matrix composites.
The polymer-matrix pbo fiber reinforced composite NOL ring sample that obtains carries out the interlayer shear performance test according to GB/T3357-82, and its shear strength value is at 26.28MPa.
Embodiment 2 is with the difference of embodiment 1: the kind of finishing agent is different, pbo fiber immerses finishing agent required time difference, the kind of curing agent is different with shared mass fraction, the quality difference of acetone in the glue, the quality and immersion asynchronism(-nization) that immerse the pbo fiber of matrix glue.
Embodiment 3: with pbo fiber immerse by mass percent be 15%, molecular weight formed in the finishing agent by 2500～3500 CTPB-styrene (HTBS) and solvent acetone, the immersion time is 6s, takes out pbo fiber after finishing from container.Preparation is by the epoxy resin E-44 of 100 parts by mass, the DDS of 30 parts by mass, and the consumption of solvent acetone is the 13% matrix glue of determining by epoxy resin mass percent in the glue, then the matrix glue is poured in the steeping vat.Making the pbo fiber of 72 parts by mass immerse the above-mentioned matrix glue immersion time is 12s, Wrapping formed on NOL ring mould, place 24h under the room temperature, then sample being put into vacuum drying chamber is cured, in vacuum be-the 0.1MPa condition under, the curing process of pbo fiber composite is: 70 ℃ are heated 2h down, are warming up to 120 ℃ of heating 2h, continue to be warming up to 180 ℃ of heating 5h.Close drying box after solidifying end, naturally cool to room temperature, the demoulding promptly gets pbo fiber and strengthens polymer matrix composites.
The polymer-matrix pbo fiber reinforced composite NOL ring sample that obtains carries out the interlayer shear performance test according to GB/T3357-82, and its shear strength value is at 27.30MPa.
Claims (5)
1. pbo fiber special surface treating agent is characterized in that: contain mass percent and be 15～30%, molecular weight be 2500～3500 contain end carboxyl liquid rubber and mass percent is 70～85% solvent acetone.
2. pbo fiber special surface treating agent according to claim 1 is characterized in that: described liquid rubber be CTPB, CTPB-styrene or CTPB-acrylonitrile any.
3. a pbo fiber that adopts the described special surface treating agent of claim 1 to handle prepares the method for composite, it is characterized in that may further comprise the steps:
(a) according to mass percent be 15～30%, molecular weight be 2500～3500 contain end carboxyl liquid rubber and mass percent is that 70～85% solvent acetone are mixed with surface conditioning agent;
(b) immersion time 8～15s is equipped with in the container of surface conditioning agent in the pbo fiber immersion;
(c) according to the epoxy resin of 100 parts by mass, add curing agent 27～32 parts by mass, adding makes the epoxy resin mass percent account for 13～16% solvent acetone, and each component mixed dissolution becomes homogeneous phase matrix glue;
(d) will immerse 6～15s in the homogeneous phase matrix glue through the pbo fiber after step (b) processing, then the pbo fiber wrapping be encircled on the mould around NOL, and place 24～30h under the room temperature and solidify;
(e) put into vacuum drying chamber again and be heating and curing, condition is heating and curing: vacuum-0.1～-0.3MPa, under 70 ℃ of conditions, be incubated 2h then, under 120 ℃ of conditions, be incubated 2h, behind insulation 5h under 180 ℃ of conditions, naturally cool to room temperature, the demoulding promptly gets the pbo fiber reinforced composite.
4. preparation method according to claim 3 is characterized in that: described epoxy resin be contain in the molecule epoxide number be 0.41～0.80 epoxy resin any or appoint several.
5. preparation method according to claim 3 is characterized in that: described curing agent be diaminodiphenyl ether, m-phenylene diamine (MPD) or diamino-diphenyl sulfone any.
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| CN2009100240057A CN101649553B (en) | 2009-09-22 | 2009-09-22 | Method for preparing PBO fibre composite material and special surface treating agent thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040096658A1 (en) * | 2002-11-14 | 2004-05-20 | Judy Chu | Subcoat for poly (p-phenylene-2,6-benzobisoxazole) fibers |
| CN101319084A (en) * | 2008-07-17 | 2008-12-10 | 上海交通大学 | Preparation method for poly-p-phenylene-benzo-dioxazole fibre/epoxy resin composite material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040096658A1 (en) * | 2002-11-14 | 2004-05-20 | Judy Chu | Subcoat for poly (p-phenylene-2,6-benzobisoxazole) fibers |
| CN101319084A (en) * | 2008-07-17 | 2008-12-10 | 上海交通大学 | Preparation method for poly-p-phenylene-benzo-dioxazole fibre/epoxy resin composite material |
Non-Patent Citations (3)
| Title |
|---|
| JP特开平6-280167A 1994.10.04 |
| S.Melcher,J.W.Liu等.Adhesion of PBO fiber in epoxy composites.《J Mater Sci 》.2007,(第42期),第8047-8049页. * |
| Sung-in Moon.A STUDY OF THE IMPACT PROPERTIES OF SURFACE-MODIFIED UHMPE-FIBER/VINYLESTER COMPOSITES.《 Composites Science and Technology》.1997,(第57期),第198页第2.2-2,5节,第202页第4节. * |
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Granted publication date: 20110817 Termination date: 20200922 |