CN106810863A - 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
- Publication number
- CN106810863A CN106810863A CN201510872720.1A CN201510872720A CN106810863A CN 106810863 A CN106810863 A CN 106810863A CN 201510872720 A CN201510872720 A CN 201510872720A CN 106810863 A CN106810863 A CN 106810863A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- mass parts
- pbo fiber
- pbo
- fiber
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to a kind of pbo fiber epoxy resin composite material and preparation method thereof, the blending epoxy matrix comprising 100 mass parts pbo fibers and 50~80 mass parts；First pre-polymerization is made sizing material；Pbo fiber is carried out into surface modification treatment；Pbo fiber is immersed in sizing material, wind, dried, obtain prepreg, prepreg is laid in mould, ladder-elevating temperature cure under pressure, room temperature is naturally cooled to afterwards, the demoulding obtains final product pbo fiber/epoxy resin composite material.The present invention has used the neo-epoxy resin and benzoxazine colophony for having excellent compatibility with PBO in matrix resin sizing material, wellability and caking property of the pbo fiber to matrix resin can be improved, so as to significantly improve the interface performance of resin and fiber, the powerful feature high of pbo fiber in composite is given full play to；And the temperature resistant grade and mechanical property of composite are increased substantially, can be used to prepare high temperature resistant composite and the composite with high intensity requirement.
Description
【Technical field】
It is a kind of pbo fiber ring specifically the present invention relates to pbo fiber technical field of composite materials
Epoxy resin composite material and preparation method thereof.
【Background technology】
Polyphenylene Benzo-dioxazole (PBO) is a class hetero-aromatic ring liquid crystal polymer containing benzothiazole, with excellent
Different mechanical property, resistance to elevated temperatures and chemical stability, are widely used in high performance material field
Prospect, in particular for high strength fibre.Pbo fiber be applied at present flak jackets, explosion-proof impact material and
The fields such as aircraft high-strength composite material.
But it is different from the high-performance fiber that other are used for composite, lack pole in PBO polymer molecular structures
Property group, causes wellability poor, and fiber is low with resin matrix interface binding power, is also easy to produce boundary defect simultaneously
Composite bending property is had a strong impact on, the powerful feature high of component pbo fiber is strengthened in composite not
Fully demonstrate out, fiber and matrix resin interface performance difference are the main weak spots of composite.Therefore,
Done numerous studies work at the surface of the pbo fiber aspect that is modified both at home and abroad, such as surface etching, coupling agent,
Corona treatment, sided corona treatment and radiation treatment etc. also achieve many achievements.
Document and patented method that current this respect has been announced, are carried out more by pbo fiber
The process of surface treatment of optimization, improves the polarity of fiber surface, introduces active group, reinforcing fiber with
Interface interaction power between resin matrix, its effect is preferable not enough.How to improve preparation has good boundary
Pbo fiber/the polymer matrix composite of face effect, is the forward position class of pbo fiber field of compound material
Topic and problem.
【The content of the invention】
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of pbo fiber epoxy resin is answered
Condensation material and preparation method thereof.
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 its raw material is：100 mass parts PBO
The blending epoxy matrix of fiber and 50~80 mass parts；
The material quality component of blending epoxy matrix is：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 matter
Amount part commodity bisphenol A-type benzoxazine colophony Ba, 2~10 mass parts benzoxazine colophony B.
Described commodity epoxy resin and commodity epoxy resin curing accelerator is what is commonly used in composite
Commercially available ordinary resin and curing agent.
Described bisphenol A-type benzoxazine colophony Ba is a kind of commercially available common benzoxazine colophony.
Described epoxy resin A, its molecular structure of chemistry formula be one of epoxy of following three kinds of structures or this
Three kinds of structure epoxies mixture in any proportion：
Or
Or
Described benzoxazine colophony B, its molecular structure of chemistry formula is the benzoxazine of following three kinds of structures
One of or these three structure benzoxazine mixtures in any proportion：
Or
Or
Wherein, R is substituted radical；Such as it is methyl etc..
A kind of preparation method of pbo fiber epoxy resin composite material, it is concretely comprised the following steps：
(1)：Pbo fiber surface modification treatment：
The surface of pbo fiber is modified and uses conventional process for modifying surface, is such as changed using pyrovinic acid
Property, to carry out surface to fiber using lower temperature plasma technology modified etc., in this respect over the last number of years
Through having substantial amounts of document and patent report；
(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 matter
Amount part commodity epoxy resin curing accelerator, 0.1~10 mass parts commodity benzoxazine, 2~10 mass parts
Benzoxazine colophony B is well mixed, and pre-polymerization 1~4 hour at 100~160 DEG C, add 50~
500 parts of acetone, is made sizing material；
(3) 100 mass parts pbo fibers are immersed in the sizing material that step (2) is obtained, wound, is dried in the air
It is dry, prepreg is obtained, prepreg is laid in mould, 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 pressures, pressure
10~20MPa is kept, room temperature is naturally cooled to afterwards, the demoulding obtains final product pbo fiber/epoxy resin and is combined
Material.
Compared with prior art, the positive effect of the present invention is：
(1) present invention has used the epoxy resin for having excellent compatibility with PBO in matrix resin sizing material
A, and in order to further enhance interfacial effect, is also added into benzoxazine colophony B, and benzoxazine and
Epoxy resin can be cross-linked with each other solidification, can improve wellability and caking property of the pbo fiber to matrix resin,
So as to significantly improve the interface performance of resin and fiber, composite interlayer shear strength (ILSS) is significantly carried
Height, reaches smoothly transmission stress, improves the effect of composite machinery performance, gives full play to composite
The powerful feature high of middle pbo fiber.
(2) at present in the preparation process of pbo fiber/composite, more using surface chemistry etching, altogether
The method such as poly- modified, coupling agent treatment, sided corona treatment and radiation treatment is surface-treated to fiber, so
It is combined with epoxy resin-base again afterwards.If it is the disadvantage is that, the insufficient strength of Fiber strength,
Then the interface performance between fiber and resin improves limited, and increases Fiber strength intensity, then fiber
Body mechanical property loss it is too big.The present invention improves fiber and resin by improving matrix resin formula
Between interface performance, pbo fiber by more low intensive surface treatment can meet composite prepare
It is required that, the intrinsic loss of energy of fiber can be prevented excessive.
(3) present invention has used resistant to elevated temperatures benzoxazine colophony and has contained in matrix resin sizing material
The epoxy resin A and benzoxazine colophony B of the oxazole ring structure of high temperature resistant, by the thermally-stabilised of oxazole ring
Property and mechanical property it is very good, therefore the polymer temperature resistant grade obtained after the mixed matrix resin solidification and
Mechanical property is increased substantially, and can be used to prepare high temperature resistant composite and answering with high intensity requirement
Condensation material.
【Brief description of the drawings】
The nucleus magnetic hydrogen spectrum figure of the epoxy resin A that Fig. 1 embodiments 1 are used；
The nucleus magnetic hydrogen spectrum figure of the benzoxazine B that Fig. 2 embodiments 1 are used.
【Specific embodiment】
A kind of specific reality of pbo fiber epoxy resin composite material of the invention presented below and preparation method thereof
Apply mode.
Embodiment 1
First by pbo fiber immersion containing in 2% pyrovinic acid solution, under the ul-trasonic irradiation of 50W,
Treatment 305min, takes out fiber, standby with distillation water washing, drying.
By 40 mass parts commodity epoxy resin E51,5 mass parts epoxy resin A, 0.5 mass parts asphalt mixtures modified by epoxy resin
Fat curing accelerator, 5 mass parts bisphenol A-type benzoxazine colophony Ba, 2.5 mass parts benzoxazine colophonies
B is well mixed, and pre-polymerization 2 hours at 120 DEG C, adds 100 parts of acetone, is made sizing material.
In the sizing material that 100 mass parts pbo fibers immersion above-mentioned steps are obtained, wind, dry, obtaining
To prepreg, prepreg is laid in mould, first the pre-heat treatment 1h at 100 DEG C, 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 pressures, pressure keeps
12~15MPa, naturally cools to room temperature afterwards, and the demoulding obtains final product pbo fiber/epoxy resin composite material.
Wherein, the epoxy resin A in the present embodiment, its molecular structure of chemistry formula is following structure：
Benzoxazine colophony B in the present embodiment, its molecular structure of chemistry formula structure：
Embodiment 2
In the present embodiment, the composition of the epoxy resin A and benzoxazine colophony B only in sizing material is different from fact
Example 1 is applied, remaining is same as Example 1.
In the present embodiment, epoxy resin A is still 5 mass parts, but consisting of the ring of following three kinds of structures
The mixture of oxygen, wherein：
It is 1 mass parts；
It is 3 mass parts；
It is 1 mass parts；
In the present embodiment, the content of benzoxazine colophony B is still 2.5 mass parts, but consisting of below
Three kinds of mixtures of the benzoxazine of structure：
It is 1 mass parts；
It is 1 mass parts；
It is 0.5 mass parts；
Embodiment 3
In the present embodiment, the composition and content of the epoxy resin A and benzoxazine colophony B only in sizing material are not
Embodiment 1 is same as, remaining is same as Example 1.
In the present embodiment, epoxy resin A is 10 mass parts, consisting of the epoxy of following three kinds of structures
Mixture, wherein：
It is 1 mass parts；
It is 7 mass parts；
It is 2 mass parts；
In the present embodiment, the content of benzoxazine colophony B is 5 mass parts, consisting of following three kinds of knots
The mixture of the benzoxazine of structure：
It is 1 mass parts；
It is 3 mass parts；
It is 1 mass parts；
Embodiment 4
In the present embodiment, proportioning is different from embodiment 3 only in sizing material, and remaining is same as Example 3.
In the present embodiment, sizing material proportioning is 55 mass parts commodity epoxy resin E51,10 mass parts asphalt mixtures modified by epoxy resin
Fat A, 0.8 mass parts epoxy resin curing accelerator, 5 mass parts benzoxazine colophony B.With embodiment 3
Unlike, be free of bisphenol A-type benzoxazine colophony Ba in matrix resin formula.
It is an advantage of the invention that the resin for having excellent compatibility with pbo fiber is introduced in matrix resin making
It is hybrid resin, wellability and caking property of the pbo fiber to matrix resin is remarkably improved, so that significantly
Improve the interface performance of resin and fiber.
The present invention used in matrix resin sizing material the neo-epoxy resin that has excellent compatibility with PBO and
Benzoxazine colophony, can improve wellability and caking property of the pbo fiber to matrix resin, so as to significantly carry
The interface performance of high resin and fiber, gives full play to the powerful feature high of pbo fiber in composite；And
The temperature resistant grade and mechanical property of composite are increased substantially, and can be used to prepare high temperature resistant composite
With the composite required with high intensity.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
Logical technical staff, without departing from the inventive concept of the premise, can also make some improvements and modifications,
These improvements and modifications also should be regarded as in protection scope of the present invention.
Claims (4)
1. a kind of pbo fiber epoxy resin composite material, it is characterised in that the quality component of its raw material is：
The blending epoxy matrix of 100 mass parts pbo fibers and 50~80 mass parts.
2. a kind of pbo fiber epoxy resin composite material as claimed in claim 1, it is characterised in that
The material quality component of blending epoxy matrix is：40~70 mass parts commodity epoxy resin, 3~15 matter
Amount part epoxy resin A, 0.5~1.5 mass parts commodity epoxy resin curing accelerator, 0.1~10 mass parts
Commodity bisphenol A-type benzoxazine colophony Ba, 2~10 mass parts benzoxazine colophony B.
3. a kind of pbo fiber epoxy resin composite material as claimed in claim 2, it is characterised in that
Described epoxy resin A, its molecular structure of chemistry formula be one of epoxy of following three kinds of structures or this
Three kinds of structure epoxies mixture in any proportion：
4. a kind of preparation method of pbo fiber epoxy resin composite material, it is characterised in that its specific step
Suddenly it is：
(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 matter
Amount part commodity epoxy resin curing accelerator, 0.1~10 mass parts commodity benzoxazine, 2~10 mass parts
Benzoxazine colophony B is well mixed, and pre-polymerization 1~4 hour at 100~160 DEG C, add 50~
500 parts of acetone, is made sizing material；
(3) 100 mass parts pbo fibers are immersed in the sizing material that step (2) is obtained, wound, is dried in the air
It is dry, prepreg is obtained, prepreg is laid in mould, 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 pressures, pressure
10~20MPa is kept, room temperature is naturally cooled to afterwards, the demoulding obtains final product pbo fiber/epoxy resin multiple
Condensation material.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106810863A true CN106810863A (en) | 2017-06-09 |
| CN106810863B CN106810863B (en) | 2019-03-29 |
Family
ID=59108007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510872720.1A Active CN106810863B (en) | 2015-12-02 | 2015-12-02 | A kind of pbo fiber epoxy resin composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106810863B (en) |
Cited By (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 |
| CN109836576A (en) * | 2019-02-25 | 2019-06-04 | 安徽工程大学 | A kind of dissaving polymer and its method for promoting fiber and epoxy resin binding performance |
| 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 |
| US11926695B2 (en) | 2019-11-14 | 2024-03-12 | Samsung Electronics Co., Ltd. | High-thermal conductive epoxy compound and composition, material for semiconductor package, molded product, electric and electronic device, and semiconductor package including the same |
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 |
|---|
| 陈艳等: "环氧树脂／PBO纤维复合材料性能研究", 《工程塑料应用》 * |
Cited By (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 |
| CN109836576A (en) * | 2019-02-25 | 2019-06-04 | 安徽工程大学 | A kind of dissaving polymer and its method for promoting fiber and epoxy resin binding performance |
| US11926695B2 (en) | 2019-11-14 | 2024-03-12 | Samsung Electronics Co., Ltd. | High-thermal conductive epoxy compound and composition, material for semiconductor package, molded product, 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106810863B (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106810863A (en) | A kind of pbo fiber epoxy resin composite material and preparation method thereof | |
| CN100564448C (en) | A kind of method for preparing molded epoxy resin sheet and products thereof | |
| CN102660874B (en) | Thermoplasticity sizing agent for carbon fiber and preparation and usage thereof | |
| CN106398119B (en) | A kind of fibre-reinforced bio-resin glue composite material and preparation method | |
| CN106633645A (en) | Carbon fiber reinforced high-strength light-weight composite material and preparation method thereof | |
| CN110256825A (en) | A kind of fiberglass reinforced fire retardant PET composite material and preparation method thereof | |
| CN112795143A (en) | High-performance pultrusion epoxy resin composite material for wind power and preparation method thereof | |
| CN101260224B (en) | Method for modifying bisphenol A epoxy resin by using liquid crystal epoxy resin | |
| CN109836557B (en) | Toughened hydrophobic epoxy resin and preparation method thereof | |
| CN103012779B (en) | Benzoxazine resin/ionic liquid composition | |
| CN106479137A (en) | A kind of high thermal conductivity PBT composite and preparation method thereof | |
| CN102994031A (en) | Epoxy adhesive | |
| CN102212322A (en) | Carbon nano tube reinforcing epoxy structural adhesive and method for preparing same | |
| CN105315649A (en) | Preparation method of PEEK composite material with high tensile strength | |
| CN107353599A (en) | A kind of wear-resisting type composite and preparation method thereof | |
| CN106883559A (en) | A kind of preparation method of high rigidity carbon fibre composite resin matrix | |
| CN106700102A (en) | Polyphenylene sulfide reinforced composite material and preparing method thereof | |
| CN106751679A (en) | A kind of carbon fiber modifying makrolon material and preparation method thereof | |
| CN105950062A (en) | Efficient waterproof binder and production method thereof | |
| CN104371499A (en) | Epoxy resin composite material for powder coating and preparation method thereof | |
| CN104059590A (en) | Room-temperature-curing toughened epoxy resin adhesive and preparation method thereof | |
| CN109749056A (en) | A kind of acid controlled degradation ketal type cycloaliphatic epoxy resin, preparation method and application | |
| CN104356597A (en) | Composite material with bagasse and modified solid epoxy resin and production method thereof | |
| CN107556609A (en) | A kind of rudder of aircraft composite and preparation method thereof | |
| CN106750933A (en) | A kind of heat resistant type metal whisker composite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |