CN1544745A - PBO fabric surface modifying process - Google Patents
PBO fabric surface modifying process Download PDFInfo
- Publication number
- CN1544745A CN1544745A CNA2003101076796A CN200310107679A CN1544745A CN 1544745 A CN1544745 A CN 1544745A CN A2003101076796 A CNA2003101076796 A CN A2003101076796A CN 200310107679 A CN200310107679 A CN 200310107679A CN 1544745 A CN1544745 A CN 1544745A
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- Prior art keywords
- pbo fiber
- fiber
- pbo
- surface modifying
- fiber surface
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000004744 fabric Substances 0.000 title 1
- 239000000835 fiber Substances 0.000 claims abstract description 97
- 239000011521 glass Substances 0.000 claims abstract description 4
- 239000004033 plastic Substances 0.000 claims abstract description 4
- 229920003023 plastic Polymers 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000006193 liquid solution Substances 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 15
- 229920000647 polyepoxide Polymers 0.000 claims description 15
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 13
- 230000005855 radiation Effects 0.000 claims description 12
- 230000005251 gamma ray Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012048 reactive intermediate Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 208000019155 Radiation injury Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- -1 polyparaphenylene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses polymer-based composite reinforced material PBO fiber surface modification processing method ---- a PBO fiber surface modifying method, implemented by the following steps: first soaking PBO fiber in a plastic or glass container with grafting body solution, then sealing the container and irradiating by gama rays, then placing for 20-30 hours, and finally taking out PBO fiber. It irradiates on the condition that the fiber substrate and the grafting solution contact directly, thus making graft copolymerization reaction. Because the grafting reaction is made only on the surface layer of the fiber, the oriented structure of PBO molecular chain is not influenced and the mechanical property of the fiber is not reduced. The yarn group coiled of PBO fiber needs no processing like separating yarn or washing, etc before and after irradiation. It has simple and convenient operation, stable process and reliable quality, applied to industrialized production.
Description
Technical field: the present invention relates to polymer matrix composite with reinforcing material PBO (being polyparaphenylene Ben Bing Er oxazole) fiber surface modification processing method.
Background technology: pbo fiber is the high-performance fiber that is made through the fiber spinning from crystalline state technology by the PBO polymer.Its TENSILE STRENGTH and modulus are about the twice of Armoc (aramid fiber) fiber.Particularly elastic modelling quantity as straight chain polymer, thinks to have limit elastic modelling quantity.The straightforward strand of steel has been given the heat resistance of pbo fiber excellence again, and is higher 100 ℃ than the heat resisting temperature of Armoc fiber, is the most excellent a kind of organic fiber of present combination property.Therefore, pbo fiber is the reinforcing material that is used to Aero-Space and civilian advanced composite material.But because the regular orientation texture of PBO polymer molecule makes fiber surface very smooth, lack horizontal connection between the polymer molecular chain, and the polarity hetero atom overwhelming majority on the strand is wrapped in fibrous inside, fiber surface polarity is also very little.Fiber surface is smooth and active low, is difficult for soaking into resin, and the interface performance that causes fiber to combine with resin matrix is poor, and interface shear strength is low.Influence the performance of composite material combination property thereby the interface of difference bonding can not be carried out the transmission of power preferably, and then restricted the application of pbo fiber in advanced field of compound material.
Summary of the invention: in order to overcome the defective of existing P BO fiber surface because of the smooth and active low interface performance difference that combines with resin matrix, provide a kind of pbo fiber surface modifying method, the interface performance that pbo fiber is combined with resin matrix is improved.The present invention is achieved by following proposal: a kind of pbo fiber surface modifying method, it is realized by following step: at first pbo fiber is immersed 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 after irradiation was finished from said vesse then.Pbo fiber under high-energy ray-gamma-ray irradiation with grafting body generation graft copolymerization, make on the fiber surface and to introduce active function groups and to increase fiber surface area, realize fiber surface modification.Because energy of height, penetration power is strong, not only can also excite grafting body compound to produce the reactive intermediate of various energy levels simultaneously by the excitation fiber cortex polymer, wherein partially grafted body reactive intermediate is grafted to fiber surface, grafting body molecule realizes that with fiber surface chemistry connects rather than more weak inferior key connecting, in addition, irradiation also can carry out etching to fiber surface, make smooth pbo fiber surface produce uneven, increased the surface area that contacts with resin matrix, add and contain the functional group that can carry out cross-linking reaction on the grafted chain molecule with epoxy resin-base, these all help the infiltration of resin matrix and crosslinked, have improved the interface performance that pbo fiber combines with resin matrix.The mutual radiation method that the present invention adopts is that fiber base material is carried out mutual radiation with the grafting liquid solution under situation about directly contacting, and makes fiber base material surface and grafting body generate active particle simultaneously in the irradiation process, thereby graft copolymerization takes place.This method free radical utilization rate height; can prevent the radiation degradation of fiber base material; on the other hand; the existence of grafting body and solvent also has the certain protection effect to the radiation injury of fiber base material; graft reaction only occurs on the cortex of fiber, and micromolecule grafting body does not enter in the cored structure of fiber, therefore; the orientation texture of PBO strand is unaffected, and the mechanical property of fiber does not reduce.The yarn group of pbo fiber institute coiled need not carry out processing such as dividing sinker or cleaning in the method for the present invention behind predose, and is easy and simple to handle, process stabilizing, and reliable in quality is applicable to suitability for industrialized production.
The specific embodiment one: the present invention realizes by following step: at first pbo fiber is immersed 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 after irradiation was finished from said vesse then.Described grafting liquid solution is that 2% to 4% epoxy resin and 96% to 98% epoxychloropropane are formed by percentage by weight.The grafting liquid solution is that 4% epoxy resin and 96% epoxychloropropane are formed by percentage by weight preferably, the influence that the grafting body is handled the pbo fiber surface property to radiation modification is very large, at first the grafting body should have the function of coupling agent, can realize the coupling reaction between fiber and the resin matrix; Moreover under gamma-radiation irradiation the grafting body can with fiber top layer molecule generation graft reaction.Selecting weight ratio is the grafting body of the grafting liquid solution formed of the epoxychloropropane of 2% to 4% epoxy resin and 96% to 98% as pbo fiber, be that epoxychloropropane is again the active good solvent of epoxy resin because epoxy resin and epoxychloropropane are the Main Ingredients and Appearances of pbo fiber composite resin matrix.Under high-energy ray irradiation, epoxide ring in epoxy resin and the epoxychloropropane is opened the generation living radical, free radical generation graft copolymerization with the generation of pbo fiber top layer, epoxy resin molecule and epoxychloropropane molecule are grafted to fiber surface, the epoxy grafted chain can participate in the chemical crosslink reaction of resin matrix when the fiber of process graft modification and resin matrix were made composite, the grafting body plays function served as bridge, thereby fiber and resin boundary surface adhesive property are improved.But because epoxy resin is easy to autohemagglutination under the high energy effect, grafting liquid concentration is not beneficial too high, and the too high epoxy resin grafting of concentration autohemagglutination chain is oversize to make the fiber surface embrittlement that hardens, so the concentration of epoxy resin is preferred 4%, to avoid the autohemagglutination of epoxy resin; On the other hand, epoxychloropropane also can be used as the graft copolymerization of participation of grafting body and pbo fiber, because the epoxychloropropane molecular weight is little, reactivity ratio's epoxy resin is big, and its graft reaction rate is also high.Because epoxychloropropane is single ring architecture, even can only produce the dimer of small-molecular weight under high-energy ray irradiation, therefore, high percent grafting does not influence the flexibility of fiber when increasing substantially the interface performance of fiber and resin matrix yet.The epoxy resin epoxychloropropane solution of low concentration is the desirable grafting liquid solution of pbo fiber.
The specific embodiment two: the difference of present embodiment and embodiment one is that the gamma-rays of employing is
60Co gamma-radiation, irradiation dose are 25～35KGy (thousand lattice are auspicious), and preferred irradiation dose is 30Kgy.Because gamma-radiation is a kind of high-energy ray, it is in initiation grafting body and fiber generation graft reaction, also can cause the variation of fiber bodies structure such as molecular chain orientation and crystal habit, can improve boundary strength though analyze irradiation theoretically, but because pbo fiber strand axial orientation degree is close to perfection, any non-axial stress or energy can be damaged the axial orientation degree of fiber molecule chain undoubtedly, irradiation also can carry out etching to fiber surface in addition, the mechanical strength that has increased the weight of fiber descends, and this just requires also will make as much as possible when improving fiber interface intensity the mechanical property loss of fiber minimum.Experiment shows when irradiation dose reaches 30kGy, boundary strength ILSS than the raising of irradiation not 130%.Continue to improve irradiation dose, high-energy ray will be greater than grafting speed to the speed of etching of fiber surface, stronger energy also can be destroyed the grafted chain that is grafted to fiber surface, causing mechanical strength obviously to descend because of stronger etching when, the ILSS value of fiber and resin matrix also can descend like this.Perhaps the ILSS value during 30kGy may also not be the peak of interface shear strength, if but continuing again to improve irradiation dose, the mechanical property of fiber can descend more, can produce unacceptable negative effect to the application of fiber.Along with the further increase of irradiation dose, irradiation then is that damage and destruction are main to the fiber embodiment, so the present invention determines that 30kGy is best irradiation dose.
The specific embodiment three: the difference of present embodiment and embodiment two is, radiation dose rate is 3.8～5.8KGy/h (thousand lattice auspicious/hour), preferred radiation dose rate 4.8KGy/h.
The specific embodiment four: the difference of present embodiment and embodiment one is that grafting liquid solution weight and pbo fiber weight ratio are 1: 1.Pbo fiber yarn group outside dimension is not more than 400mm, highly is not more than 500mm, and guarantees that silvalin group is fully immersed in the grafting liquid, soaks under the room temperature and guarantees that fiber soaked into after the grafting liquid solution in 2 hours, and airtight container carries out mutual radiation again.Fiber continued to be immersed in the grafting liquid solution 24 hours after irradiation was finished, and took out the back in lucifuge place nature airing, was stored in shady and cool dry place.The ILSS value of the fibrous composite before the modification is 11.2MPa, and the pbo fiber composite material interface intensity I LSS after modification is handled reaches 25MPa, increase rate 126%.After 6 months, the ILSS value of fibrous composite is 24MPa, and strength retention is 96%, and still the IFSS value than the fibrous composite before the modification improves 114%.Therefore, the fiber surface activity shelf-life is decided to be 6 months behind the radiation modification.Need the ILSS value of detection fibers composite again after 6 months, require or continue use or radiation treatment again according to practical use.
Claims (8)
1, a kind of pbo fiber surface modifying method, it is characterized in that it realizes by following step: at first pbo fiber is immersed 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 after irradiation was finished from said vesse then.
2, a kind of pbo fiber surface modifying method according to claim 1 is characterized in that described grafting liquid solution is that 2% to 4% epoxy resin and 96% to 98% epoxychloropropane are formed by percentage by weight.
3, a kind of pbo fiber surface modifying method according to claim 2 is characterized in that the grafting liquid solution is that 4% epoxy resin and 96% epoxychloropropane are formed by percentage by weight preferably.
4, a kind of pbo fiber surface modifying method according to claim 1 is characterized in that the gamma-rays that adopts is
60Co gamma-radiation, irradiation dose are 25～35KGy.
5, a kind of pbo fiber surface modifying method according to claim 4 is characterized in that preferred irradiation dose is 30Kgy.
6, a kind of pbo fiber surface modifying method according to claim 4 is characterized in that radiation dose rate is 3.8～5.8KGy/h.
7, a kind of pbo fiber surface modifying method according to claim 6 is characterized in that preferred radiation dose rate 4.8KGy/h.
8, a kind of pbo fiber surface modifying method according to claim 1, it is characterized in that grafting liquid solution weight and pbo fiber weight ratio are 1: 1, pbo fiber yarn group outside dimension is not more than 400mm, highly be not more than 500mm, and guarantee that silvalin group is fully immersed in the grafting liquid, and soaking under the room temperature and guaranteed that fiber soaked into after the grafting liquid solution in 2 hours, airtight container carries out mutual radiation again, fiber continued to be immersed in the grafting liquid solution 24 hours after irradiation was finished, and took out the back in lucifuge place nature airing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310107679 CN1236133C (en) | 2003-11-11 | 2003-11-11 | PBO fabric surface modifying process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310107679 CN1236133C (en) | 2003-11-11 | 2003-11-11 | PBO fabric surface modifying process |
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| Publication Number | Publication Date |
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| CN1544745A true CN1544745A (en) | 2004-11-10 |
| CN1236133C CN1236133C (en) | 2006-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310107679 Expired - Lifetime CN1236133C (en) | 2003-11-11 | 2003-11-11 | PBO fabric surface modifying process |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355687C (en) * | 2005-10-21 | 2007-12-19 | 哈尔滨工业大学 | Surface modification method of quartz fiber |
| CN101445613B (en) * | 2008-12-16 | 2011-06-22 | 大连理工大学 | Interface modification method of poly(p-phenylene-benzobisoxazole) fiber-reinforced soluble polyaryl ether resin composite material |
| CN103015161A (en) * | 2013-01-23 | 2013-04-03 | 哈尔滨工业大学 | Method for modifying compression performance of PBO (poly (p-phenylene-2, 6-benzobisoxazole)) fiber |
| CN103276586A (en) * | 2013-05-31 | 2013-09-04 | 哈尔滨工业大学 | Surface modification method for M40J graphite fibers |
| CN103849145A (en) * | 2013-12-20 | 2014-06-11 | 上海珀理玫化学科技有限公司 | Formula of synthesizing PBO (poly-p-phenylene benzobisoxazole) fibrous composite material |
| CN104212125A (en) * | 2014-09-04 | 2014-12-17 | 哈尔滨哈玻拓普复合材料有限公司 | High-dielectric-property composite material for low-frequency mobile load radar dome and preparation method thereof |
| CN105755803A (en) * | 2016-04-19 | 2016-07-13 | 西安工程大学 | PBO (poly-p-phenylene benzobisoxazole) fiber molecular structure modification method |
| CN108610630A (en) * | 2018-05-14 | 2018-10-02 | 哈尔滨工业大学 | A kind of preparation method of high temperature dielectric properties pbo fiber composite material |
| CN109295690A (en) * | 2018-10-09 | 2019-02-01 | 哈尔滨工业大学 | A kind of resistance to ultraviolet/construction method of the anti-atomic oxygen nanometer containing silicon coating in pbo fiber surface |
-
2003
- 2003-11-11 CN CN 200310107679 patent/CN1236133C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355687C (en) * | 2005-10-21 | 2007-12-19 | 哈尔滨工业大学 | Surface modification method of quartz fiber |
| CN101445613B (en) * | 2008-12-16 | 2011-06-22 | 大连理工大学 | Interface modification method of poly(p-phenylene-benzobisoxazole) fiber-reinforced soluble polyaryl ether resin composite material |
| CN103015161A (en) * | 2013-01-23 | 2013-04-03 | 哈尔滨工业大学 | Method for modifying compression performance of PBO (poly (p-phenylene-2, 6-benzobisoxazole)) fiber |
| CN103015161B (en) * | 2013-01-23 | 2015-11-11 | 哈尔滨工业大学 | A kind of pbo fiber compression performance method of modifying |
| CN103276586A (en) * | 2013-05-31 | 2013-09-04 | 哈尔滨工业大学 | Surface modification method for M40J graphite fibers |
| CN103276586B (en) * | 2013-05-31 | 2015-01-21 | 哈尔滨工业大学 | Surface modification method for M40J graphite fibers |
| CN103849145A (en) * | 2013-12-20 | 2014-06-11 | 上海珀理玫化学科技有限公司 | Formula of synthesizing PBO (poly-p-phenylene benzobisoxazole) fibrous composite material |
| CN104212125A (en) * | 2014-09-04 | 2014-12-17 | 哈尔滨哈玻拓普复合材料有限公司 | High-dielectric-property composite material for low-frequency mobile load radar dome and preparation method thereof |
| CN105755803A (en) * | 2016-04-19 | 2016-07-13 | 西安工程大学 | PBO (poly-p-phenylene benzobisoxazole) fiber molecular structure modification method |
| CN108610630A (en) * | 2018-05-14 | 2018-10-02 | 哈尔滨工业大学 | A kind of preparation method of high temperature dielectric properties pbo fiber composite material |
| CN108610630B (en) * | 2018-05-14 | 2020-07-28 | 哈尔滨工业大学 | Preparation method of PBO fiber composite material with high-temperature dielectric property |
| CN109295690A (en) * | 2018-10-09 | 2019-02-01 | 哈尔滨工业大学 | A kind of resistance to ultraviolet/construction method of the anti-atomic oxygen nanometer containing silicon coating in pbo fiber surface |
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| Publication number | Publication date |
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| CN1236133C (en) | 2006-01-11 |
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Application publication date: 20041110 Assignee: HARBIN TOPFRP COMPOSITE Co.,Ltd. Assignor: Harbin Institute of Technology Contract record no.: 2012230001673 Denomination of invention: PBO fabric surface modifying process Granted publication date: 20060111 License type: Common License Record date: 20120920 |
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