CN106810863B - A kind of pbo fiber epoxy resin composite material and preparation method thereof - Google Patents
A kind of pbo fiber epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN106810863B CN106810863B CN201510872720.1A CN201510872720A CN106810863B CN 106810863 B CN106810863 B CN 106810863B CN 201510872720 A CN201510872720 A CN 201510872720A CN 106810863 B CN106810863 B CN 106810863B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical & Material Sciences (AREA)
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Abstract
The present invention relates to a kind of pbo fiber epoxy resin composite materials and preparation method thereof, the blending epoxy matrix comprising 100 mass parts pbo fibers and 50~80 mass parts；Sizing material is made in first pre-polymerization；Pbo fiber is subjected to surface modification treatment；Pbo fiber is immersed in sizing material, wind, is dried, prepreg is obtained, prepreg is laid in mold, ladder-elevating temperature cure under pressure naturally cools to room temperature later, demoulds to get pbo fiber/epoxy resin composite material.The present invention has used and the PBO neo-epoxy resin for having excellent compatibility and benzoxazine resin in matrix resin sizing material, pbo fiber can be improved to the wellability and caking property of matrix resin, to significantly improve the interface performance of resin and fiber, the high strength characteristics of pbo fiber in composite material are given full play to；And the temperature resistant grade and mechanical property of composite material increase substantially, the composite material that can be used for preparing high temperature resistant composite and require with high intensity.
Description
[technical field]
The present invention relates to pbo fiber technical field of composite materials, specifically, being that a kind of pbo fiber epoxy resin is compound
Material and preparation method thereof.
[background technique]
Polyphenylene benzo dioxazole (PBO) is a kind of hetero-aromatic ring liquid crystal polymer containing benzothiazole, has excellent mechanics
Performance, high temperature resistance and chemical stability have wide practical use in high performance material field, in particular for high intensity
Fiber.Pbo fiber is applied to the fields such as flak jackets, explosion-proof impact material and aircraft high-strength composite material at present.
But it is different for the high-performance fiber of composite material from other, lack polar group in PBO polymer molecular structure,
Cause wellability poor, fiber is low with resin matrix interface binding power, is also easy to produce boundary defect and seriously affects composite material bending
Performance, the high strength characteristics for enhancing component pbo fiber in composite material do not fully demonstrate out, and fiber and matrix resin are interface characteristics
Energy difference is the main weak spot of composite material.For this purpose, having done numerous studies work in terms of the surface modification of pbo fiber both at home and abroad
Make, such as surface etching, coupling agent, corona treatment, sided corona treatment and radiation treatment also achieve many achievements.
The document and patented method that this respect has been announced at present are mostly by carrying out more optimized table to pbo fiber
Surface treatment technique improves the polarity of fiber surface, introduces active group, the interface interaction between reinforcing fiber and resin matrix
Power, effect are ideal not enough.Pbo fiber/polymer matrix composite that preparation has good interface effect how is improved, is
The advanced subject and problem of pbo fiber field of compound material.
[summary of the invention]
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of pbo fiber epoxy resin composite material and
Preparation method.
The purpose of the present invention is achieved through the following technical solutions:
A kind of pbo fiber epoxy resin composite material, the quality component of raw material are as follows: 100 mass parts pbo fibers and 50~
The blending epoxy matrix of 80 mass parts；
The material quality component of blending epoxy matrix are as follows: 40~70 mass parts commodity epoxy resin, 3~15 mass parts
Epoxy resin A, 0.5~1.5 mass parts commodity epoxy resin curing accelerator, 0.1~10 mass parts commodity bisphenol A-type benzo are disliked
Piperazine resin B a, 2~10 mass parts benzoxazine resin B.
The commodity epoxy resin and commodity epoxy resin curing accelerator is common commercially available general in composite material
Logical resin and curing agent.
The bisphenol A-type benzoxazine resin Ba is a kind of commercially available common benzoxazine resin.
The epoxy resin A, molecular structure of chemistry formula are one of epoxy of following three kinds of structures or these three structures
The mixture of epoxy in any proportion:
Or
Or
The benzoxazine resin B, molecular structure of chemistry formula be following three kinds of structures one of benzoxazine or this
The mixture of three kinds of structure benzoxazines in any proportion:
Or
Or
Wherein, R is substituent group；It for example is methyl etc..
A kind of preparation method of pbo fiber epoxy resin composite material, the specific steps are that:
(1): pbo fiber surface modification treatment:
The surface modification of pbo fiber uses conventional process for modifying surface, such as using methane sulfonic acid modification, using low
Isothermal plasma technology carries out surface modification etc. to fiber, has there is a large amount of document and patent report over the last number of years in this respect
Road；
(2) prepared by matrix resin sizing material:
By 40~70 mass parts commodity epoxy resin, 3~15 mass parts epoxy resin A, 0.5~1.5 mass parts commodity ring
Oxygen solidified resin promoter, 0.1~10 mass parts commodity benzoxazine, 2~10 mass parts benzoxazine resin B are uniformly mixed,
And pre-polymerization 1~4 hour at 100~160 DEG C, 50~500 parts of acetone is added, sizing material is made；
(3) 100 mass parts pbo fibers are immersed in the sizing material that step (2) obtain, wound, dried, obtain prepreg, it will
Prepreg is laid in mold, and first the pre-heat treatment 1h at 100 DEG C, then presses 130 DEG C/1h+140 DEG C/2h+150 DEG C/2h+170
DEG C/1h+180 DEG C/0.5h ladder-elevating temperature cure under pressure, pressure keep 10~20MPa, naturally cool to room temperature later, demould, i.e.,
Obtain pbo fiber/epoxy resin composite material.
Compared with prior art, the positive effect of the present invention is:
(1) present invention has used the epoxy resin A for having excellent compatibility with PBO in matrix resin sizing material, and in order to
Interfacial effect is further enhanced, benzoxazine resin B is also added into, and benzoxazine and epoxy resin can be cross-linked with each other admittedly
Change, pbo fiber can be improved to the wellability and caking property of matrix resin, so that the interface performance of resin and fiber is significantly improved,
Composite material interlayer shear strength (ILSS) significantly improves, and reaches smoothly transmitting stress, improves the effect of composite material machinery performance
Fruit gives full play to the high strength characteristics of pbo fiber in composite material.
(2) at present in pbo fiber/composite material preparation process, surface chemistry etching, modification by copolymerization, idol are mostly used
The methods of connection agent processing, sided corona treatment and radiation treatment are surface-treated fiber, then carry out again with epoxy resin-base
It is compound.Its shortcoming is that interface performance improvement between fiber and resin has if the intensity of Fiber strength is inadequate
Limit, and increase Fiber strength intensity, then the ontology mechanical property loss of fiber is too big.The present invention is by improving matrix resin
It is formulated to improve the interface performance between fiber and resin, pbo fiber can meet compound by more low intensive surface treatment
Material preparation requires, and the loss of fiber intrinsic performance can be prevented excessive.
(3) present invention has used benzoxazine resin resistant to high temperature in matrix resin sizing material and containing resistant to high temperature
The epoxy resin A and benzoxazine resin B of oxazole ring structure, since the thermal stability and mechanical property of oxazole ring are very good, because
The polymer temperature resistant grade and mechanical property obtained after this mixed matrix resin solidification increases substantially, and can be used for preparing resistance to
High-temperature composite material and the composite material required with high intensity.
[Detailed description of the invention]
The nucleus magnetic hydrogen spectrum figure for the epoxy resin A that Fig. 1 embodiment 1 uses；
The nucleus magnetic hydrogen spectrum figure for the benzoxazine B that Fig. 2 embodiment 1 uses.
[specific embodiment]
A kind of specific embodiment of pbo fiber epoxy resin composite material of the present invention presented below and preparation method thereof.
Embodiment 1
Pbo fiber is immersed containing in 2% methanesulfonic acid solution first, under the ultrasonic wave effect of 50W, is handled
305min takes out fiber, is washed with distilled water, dries, spare.
40 mass parts commodity epoxy resin E51,5 mass parts epoxy resin A, 0.5 mass parts epoxy resin cure are promoted
Agent, 5 mass parts bisphenol A-type benzoxazine resin Ba, 2.5 mass parts benzoxazine resin B are uniformly mixed, and pre- at 120 DEG C
Poly- 2 hours, 100 parts of acetone is added, sizing material is made.
100 mass parts pbo fibers are immersed in the sizing material that above-mentioned steps obtain, wind, are dried, prepreg is obtained, it will be pre-
Leaching material be laid in mold, first at 100 DEG C the pre-heat treatment 1h, then by 130 DEG C/1h+140 DEG C/2h+150 DEG C/2h+170 DEG C/
1h+180 DEG C/0.5h ladder-elevating temperature cure under pressure, pressure keep 12~15MPa, naturally cool to room temperature later, demoulding to get
Pbo fiber/epoxy resin composite material.
Wherein, the epoxy resin A in the present embodiment, molecular structure of chemistry formula are with flowering structure:
Benzoxazine resin B in the present embodiment, molecular structure of chemistry formula structure:
Embodiment 2
In the present embodiment, only the composition of the epoxy resin A in sizing material and benzoxazine resin B is different from embodiment 1, remaining
It is same as Example 1.
In the present embodiment, epoxy resin A is still 5 mass parts, but consisting of the epoxy of following three kinds of structures mixture,
Wherein:
For 1 mass parts；
For 3 mass parts；
For 1 mass parts；
In the present embodiment, the content of benzoxazine resin B is still 2.5 mass parts, but consisting of following three kinds of structures
The mixture of benzoxazine:
For 1 mass parts；
For 1 mass parts；
For 0.5 mass parts；
Embodiment 3
In the present embodiment, only the composition of the epoxy resin A in sizing material and benzoxazine resin B and content are different from embodiment
1, remaining is same as Example 1.
In the present embodiment, epoxy resin A is 10 mass parts, consisting of the mixture of the epoxy of following three kinds of structures,
In:
For 1 mass parts；
For 7 mass parts；
For 2 mass parts；
In the present embodiment, the content of benzoxazine resin B is 5 mass parts, consisting of the benzo of following three kinds of structures is disliked
The mixture of piperazine:
For 1 mass parts；
For 3 mass parts；
For 1 mass parts；
Embodiment 4
In the present embodiment, only proportion is different from embodiment 3 in sizing material, remaining is same as Example 3.
In the present embodiment, sizing material proportion is 55 mass parts commodity epoxy resin E51,10 mass parts epoxy resin A, 0.8 matter
Measure part epoxy resin curing accelerator, 5 mass parts benzoxazine resin B.As different from Example 3, in matrix resin formula
Without bisphenol A-type benzoxazine resin Ba.
It is an advantage of the invention that introduce in matrix resin has the resin of excellent compatibility as compound tree with pbo fiber
Rouge is remarkably improved pbo fiber to the wellability and caking property of matrix resin, to significantly improve the interface characteristics of resin and fiber
Energy.
The present invention has used and the PBO neo-epoxy resin for having excellent compatibility and benzoxazine in matrix resin sizing material
Pbo fiber can be improved to the wellability and caking property of matrix resin in resin, to significantly improve the interface characteristics of resin and fiber
Can, give full play to the high strength characteristics of pbo fiber in composite material；And the temperature resistant grade and mechanical property of composite material are substantially
Degree improves, the composite material that can be used for preparing high temperature resistant composite and require with high intensity.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (2)
1. a kind of pbo fiber epoxy resin composite material, which is characterized in that the quality component of its raw material are as follows: 100 mass parts PBO
The blending epoxy matrix of fiber and 50~80 mass parts；
The material quality component of blending epoxy matrix are as follows: 40~70 mass parts commodity epoxy resin, 3~15 mass parts epoxies
Resin A, 0.5~1.5 mass parts commodity epoxy resin curing accelerator, 0.1~10 mass parts commodity bisphenol A-type benzoxazine tree
Rouge Ba, 2~10 mass parts benzoxazine resin B；
The epoxy resin A, molecular structure of chemistry formula are one of epoxy of following three kinds of structures or these three structure epoxies
Mixture in any proportion:
The benzoxazine resin B, molecular structure of chemistry formula be following three kinds of structures one of or these three structures by appoint
The mixture of meaning ratio:
2. a kind of preparation method of pbo fiber epoxy resin composite material, which is characterized in that the specific steps are that:
(1) pbo fiber surface modification treatment:
(2) prepared by matrix resin sizing material:
By 40~70 mass parts commodity epoxy resin, 3~15 mass parts epoxy resin A, 0.5~1.5 mass parts commodity asphalt mixtures modified by epoxy resin
Rouge curing accelerator, 0.1~10 mass parts commodity benzoxazine, 2~10 mass parts benzoxazine resin B are uniformly mixed, and
Pre-polymerization 1~4 hour at 100~160 DEG C, adds 50~500 parts of acetone, sizing material is made；
(3) 100 mass parts pbo fibers are immersed in the sizing material that step (2) obtain, wound, dried, obtained prepreg, will presoak
Material is laid in mold, and first the pre-heat treatment 1h at 100 DEG C, then presses 130 DEG C/1h+140 DEG C/2h+150 DEG C/2h+170 DEG C/1h+
180 DEG C/0.5h ladder-elevating temperature cure under pressure, pressure keep 10~20MPa, naturally cool to room temperature later, demould to get PBO
Fiber/epoxy resin composite material；
The epoxy resin A, molecular structure of chemistry formula are one of epoxy of following three kinds of structures or these three structure epoxies
Mixture in any proportion:
The benzoxazine resin B, molecular structure of chemistry formula be following three kinds of structures one of or these three structures by appoint
The mixture of meaning ratio:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510872720.1A CN106810863B (en) | 2015-12-02 | 2015-12-02 | A kind of pbo fiber epoxy resin composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510872720.1A CN106810863B (en) | 2015-12-02 | 2015-12-02 | A kind of pbo fiber epoxy resin composite material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106810863A CN106810863A (en) | 2017-06-09 |
| CN106810863B true CN106810863B (en) | 2019-03-29 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108000905A (en) * | 2017-12-14 | 2018-05-08 | 郑州四维特种材料有限责任公司 | A kind of pbo fiber composite material boring bar and preparation method thereof |
| CN109836576B (en) * | 2019-02-25 | 2021-12-28 | 安徽工程大学 | Hyperbranched polymer and method for improving bonding performance of fiber and epoxy resin by using same |
| KR20210058569A (en) | 2019-11-14 | 2021-05-24 | 삼성전자주식회사 | High thermal conductive epoxy compound, and composition, material for semiconductor package, molded propuct, electric and electronic device and semiconductor package including the same |
| CN111286986A (en) * | 2020-03-31 | 2020-06-16 | 西安工程大学 | PBO/high-modulus CF composite material and preparation method thereof |
| CN111534048A (en) * | 2020-04-09 | 2020-08-14 | 上海大学 | Thermosetting resin-based PBO fiber composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013223995A (en) * | 2012-04-23 | 2013-10-31 | Nippon Steel & Sumikin Materials Co Ltd | Method of manufacturing flat fiber reinforced plastic lattice shaped bar and flat fiber reinforced plastic lattice shaped bar |
| CN104650542A (en) * | 2015-01-16 | 2015-05-27 | 中航复合材料有限责任公司 | Colorless transparent epoxy resin for prepreg and method for preparing composite material |
-
2015
- 2015-12-02 CN CN201510872720.1A patent/CN106810863B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013223995A (en) * | 2012-04-23 | 2013-10-31 | Nippon Steel & Sumikin Materials Co Ltd | Method of manufacturing flat fiber reinforced plastic lattice shaped bar and flat fiber reinforced plastic lattice shaped bar |
| CN104650542A (en) * | 2015-01-16 | 2015-05-27 | 中航复合材料有限责任公司 | Colorless transparent epoxy resin for prepreg and method for preparing composite material |
Non-Patent Citations (1)
| Title |
|---|
| 环氧树脂／PBO纤维复合材料性能研究;陈艳等;《工程塑料应用》;20070903;第1卷;23-25页 |
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