CN108442122A - Sizing agent for preparing quartz fiber/nitrile resin composite material - Google Patents
Sizing agent for preparing quartz fiber/nitrile resin composite material Download PDFInfo
- Publication number
- CN108442122A CN108442122A CN201810383119.XA CN201810383119A CN108442122A CN 108442122 A CN108442122 A CN 108442122A CN 201810383119 A CN201810383119 A CN 201810383119A CN 108442122 A CN108442122 A CN 108442122A
- Authority
- CN
- China
- Prior art keywords
- composite material
- sizing agent
- nitrile
- resin composite
- quartz fibre
- 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.)
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
A sizing agent for preparing a quartz fiber/nitrile resin composite material comprises a coupling agent, nitrile resin, a catalyst and an organic solvent. Wherein the coupling agent is a silicone chain polymer; the nitrile-based resin is one or more of nitrile-based oligomer of p-phenylene ether ketone chain segment, bisphenol A type nitrile-based monomer, phosphorus-containing aryl ether nitrile oligomer, alkyne-containing aryl ether chain segment phthalonitrile resin and the like; the catalyst is 4-aminophenoxy phthalonitrile resin; the organic solvent is one or more of acetone, tetrahydrofuran, DMF, ethyl acetate, butanone and the like; the mass ratio of the coupling agent to the nitrile resin to the catalyst to the organic solvent is 5-20: 5-30: 5-20: 100. the cross-linked condensate of the sizing agent has excellent high-temperature resistance, and can improve the temperature resistance of the quartz fiber-nitrile resin interface phase, thereby improving the overall performance of the composite material at high temperature; in addition, the sizing agent is simple and easy to prepare, and is suitable for industrial production and use.
Description
Technical field
The invention belongs to high temperature resistant quartz fibre prepare and applied technical field, be related to one kind be used to prepare quartz fibre/
The sizing agent of Nitrile resin composite material.
Background technology
Quartz fibre is a kind of development situation of high-performance inorganic fibers, and main component is high-purity silicon dioxide.It maintains solid
The partial properties and feature of quartz, as Burning corrosion resistance is strong, temperature tolerance is good, thermal conductivity is low, and chemical stability is high, dielectric properties
It is more excellent.Quartz fibre has good comprehensive performance, can be used in preparing a variety of composite materials.Due to its excellent dielectric
Performance is currently that most reinforcing fibers is applied in domestic and international wave-penetrating composite material.When preparing electromagnetic wave transparent material, with the liter of temperature
Height, elasticity modulus accordingly increase, accordingly ensure that electromagnetic wave transparent material, while with higher wave transmission rate, mechanical property will not
It declines to a great extent.Therefore in high temperature wave transparent field, quartz fibre is widely applied.
Cyano resin is a kind of novel thermosetting resin, has excellent high temperature resistance, dielectric properties and good
Mechanical property is widely used in the fields such as Aeronautics and Astronautics.Especially excellent high-temperature stability, by nitrile group-containing resin and quartz
Fiber composite, can the excellent novel fire resistant electromagnetic wave transparent material of processability.
Matrix and the transition zone for enhancing the composition that is in contact in composite material, being one layer has certain thickness, structure with matrix
With reinforcement and one interface phase of cenotype that is different, having significant difference with two-phase.Its not simple geometrical plane, including two
The Three Dimensional Interface phase of transitional region between phase.It is link enhancement phase and matrix phase " tie " and stress and other information
The bridge of transmission.Therefore, quartz fibre can be all surface-treated before application is reinforcement, for example impregnate sizing agent, boundary
Face modifying agent improves wellability, interfacial adhesion, the temperature tolerance etc. with resin to improve interface, with reach finally improve it is compound
The purpose of material overall performance.But be directed to novel high temperature resistant composite-quartz fibre/cyano resin, currently without with
The adaptable sizing agent of the system.And it is temporarily also had not been reported using cyano resin as the research of sizing agent.
Invention content
In view of the deficiencies of the prior art, the present invention is multiple for this novel high temperature resistant of quartz fibre/cyano resin, wave transparent
Condensation material, provide a kind of and quartz fibre/Nitrile resin composite material adaptation prepares quartz fibre/Nitrile resin composite material
Sizing agent improves overall mechanical properties, the heat resistance of composite material to improve the two interface performance.
The technical scheme is that a kind of sizing agent being used to prepare quartz fibre/Nitrile resin composite material, it is wrapped
Coupling agent, cyano resin, catalyst and organic solvent are included,
Further, above-mentioned coupling agent is the silica chain polymerization object with general formula shown in formula 1：
In formula：The number-average molecular weight of the oligomer is 7000~13000.In this molecular weight ranges, m：N generally 7~
In the range of 11.M is the number of iterations of the silica chain structure of phthalonitrile side chain；N is the silica link containing thiol side chain
The number of iterations of structure.
Further, the number-average molecular weight of above-mentioned coupling agent is 7000~13000.
Further, above-mentioned cyano resin is one or more mixing in 4 kinds of chemicals represented by II-formula of formula V
Object：
Further, above-mentioned catalyst is 4- amino phenoxy phthalonitrile resins.
Further, above-mentioned organic solvent is one or more in acetone, tetrahydrofuran, DMF, ethyl acetate, butanone etc..
Further, the mass ratio of above-mentioned coupling agent, cyano resin, catalyst and organic solvent is 5-20：5-30：5-
20：100.
It is highly preferred that the present invention provides a kind of sizing agent being used to prepare quartz fibre/Nitrile resin composite material,
The mass fraction of formula composition and each component is：
It is highly preferred that the present invention provides a kind of sizing agent being used to prepare quartz fibre/Nitrile resin composite material,
The mass fraction of formula composition and each component is：
The preparation method of the invention sizing agent is as follows：Coupling agent is weighed according to required proportioning, cyano resin, catalyst, is had
Solvent, stirring, is prepared into clear solution, as the sizing agent.
All chemical substances referred in formula of sizing agent of the present invention can be obtained by open approach.
The present invention has the following advantages：
The present invention provides the applicable sizing agents of quartz fibre/cyano resin this advanced composite material (ACM)；The coupling used
Agent one end is silica chain, can be combined with silica quartz fibre as main component, and the other end is phthalonitrile, can be with
Cyano resin combines, and participates in the cross-linking reaction of cyano resin, and the bridge connection function on surface both to play improves interface
Cementability promotes the overall mechanical properties of composite material；The cyano resin of appropriate Rational structure is added, keeps the crosslinking of the resin solid
Compound has excellent high temperature resistance, while can improve the binding performance between the quartz fibre and cyano resin interface, to
Promote the overall performance of composite material at high temperature；In addition the sizing agent is simple, easily prepares, and is suitable for industrialized production and uses.
Description of the drawings
From the detailed description below in conjunction with the accompanying drawings to the embodiment of the present invention, these and/or other aspects of the invention and
Advantage will become clearer and be easier to understand, wherein：
The sizing agent for being used to prepare quartz fibre/Nitrile resin composite material of Fig. 1 preferred embodiment of the present invention preparation is solid
The DMA figures of solidfied material after change.
Specific implementation mode
In order to make those skilled in the art more fully understand the present invention, with reference to the accompanying drawings and detailed description to this hair
It is bright to be described in further detail.Here it is to be noted that it in the accompanying drawings, the imparting of identical reference numeral is substantially had
The component part of same or like structure and function, and will omit about their repeated description.
The dosage of each substance is mass ratio in following specific examples.
Embodiment 1：
A kind of sizing agent being used to prepare quartz fibre/Nitrile resin composite material, it includes claiming by following mass fractions
Each raw material taken：
Then above-mentioned substance is mixed, stirs, is dissolved as clear solution, that is, obtains the high temperature resistant cyano resin type starching
Agent.
Fig. 1 is to be configured by the component in embodiment 1 in addition to the solvents, the DMA figures of gained solidfied material after being heating and curing, from figure
It can be seen that the glass transition temperature of the solidfied material, which is 410 DEG C, is far above the various sizing agents, size, boundary referred in current patent
The glass transition temperature of face modifying agent.Stereoscan photograph shows that the quartz fiber surface burr after sizing agent immersion is aobvious
It writes and reduces, sizing agent plays cladding and protective effect well to fiber surface.Simultaneously by cyano resin in the embodiment, urge
The interlaminar shear strength for the composite material that agent formula is prepared with quartz textile is 30MPa, higher than nearly 400 DEG C of temperature tolerance
The interlaminar shear strength of fire resistant resin quartz fibre composite material illustrates that the sizing agent and quartz fibre have excellent interface to tie
Close performance.
Embodiment 2：
A kind of sizing agent being used to prepare quartz fibre/Nitrile resin composite material, it includes claiming by following mass fractions
Each raw material taken：
Then above-mentioned substance is mixed, stirs, is dissolved as clear solution, that is, obtains the high temperature resistant cyano resin type starching
Agent.
By the component of the configuration of embodiment 2 in addition to the solvents, the glass transition temperature of gained solidfied material is reachable after being heating and curing
380 DEG C, far above the glass transition temperature of the various sizing agents, size, interface modifier that are referred in current patent.Scanning electron microscope
Photo shows that the quartz fiber surface burr after sizing agent immersion substantially reduces, and sizing agent plays fiber surface
Cladding and protective effect well.It is prepared simultaneously by cyano resin, catalyst formulation and quartz textile in the embodiment
The interlaminar shear strength of composite material is 31MPa, is higher than the fire resistant resin quartz fibre composite material of nearly 400 DEG C of temperature tolerance
Interlaminar shear strength illustrates that the sizing agent and quartz fibre have excellent interfacial combined function.
As can be seen that present inventor is after series of studies, it is proposed that sizing agent scheme above, the application's
Scheme is not only effectively utilized the heat-resisting quantity of cyano resin, while being effectively improved the interfacial combined function with quartz fibre, especially
It is suitable for quartz fibre/Nitrile resin composite material systems.
The above embodiments are only used as embodiment of the present invention example rather than as limitations, can take other forms.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and it is also not necessarily limited to institute
Each embodiment disclosed.Without departing from the scope and spirit of illustrated each embodiment, for the art
Many modifications and changes will be apparent from for those of ordinary skill.Therefore, protection scope of the present invention should be with right
It is required that protection domain subject to.
Claims (9)
1. a kind of sizing agent being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that it include coupling agent,
Cyano resin, catalyst and organic solvent.
2. the sizing agent as described in claim 1 for being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that
The coupling agent is the silica chain polymerization object with general formula shown in formula I：
In formula：M is the number of iterations of the silica chain structure of phthalonitrile side chain；N is the silica chain structure containing thiol side chain
Number of iterations.
3. the sizing agent as claimed in claim 2 for being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that
The number-average molecular weight of the coupling agent is 7000~13000, and m：N is in the range of 7~11.
4. the sizing agent as claimed in claim 3 for being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that
The cyano resin is one or more mixtures in 4 kinds of chemicals represented by II-formula of formula V：
5. the sizing agent as claimed in claim 4 for being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that
The catalyst is 4- amino phenoxy phthalonitrile resins.
6. the sizing agent as claimed in claim 5 for being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that
The organic solvent is one or more in acetone, tetrahydrofuran, DMF, ethyl acetate, butanone etc..
7. the sizing agent as claimed in claim 6 for being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that
The coupling agent, cyano resin, catalyst and organic solvent mass ratio be 5~20：5~30：5~20：100.
8. the sizing agent as claimed in claim 7 for being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that
The mass fraction of its formula composition and each component is：
9. the sizing agent as claimed in claim 7 for being used to prepare quartz fibre/Nitrile resin composite material, which is characterized in that
The mass fraction of its formula composition and each component is：
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810383119.XA CN108442122B (en) | 2018-04-26 | 2018-04-26 | Sizing agent for preparing quartz fiber/nitrile resin composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810383119.XA CN108442122B (en) | 2018-04-26 | 2018-04-26 | Sizing agent for preparing quartz fiber/nitrile resin composite material |
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|---|---|
| CN108442122A true CN108442122A (en) | 2018-08-24 |
| CN108442122B CN108442122B (en) | 2019-08-27 |
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| CN201810383119.XA Active CN108442122B (en) | 2018-04-26 | 2018-04-26 | Sizing agent for preparing quartz fiber/nitrile resin composite material |
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Citations (10)
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|---|---|---|---|---|
| US20080255287A1 (en) * | 2007-04-13 | 2008-10-16 | The Government Of The Us, As Represented By The Secrectary Of The Navy | Phosphine oxide containing phthalonitriles |
| US20090069484A1 (en) * | 2007-09-06 | 2009-03-12 | The Government Of The Us, As Represented By The Secretary Of The Navy | Aromatic ether and alkynyl containing phthalonitriles |
| JP2010229572A (en) * | 2009-03-26 | 2010-10-14 | Toho Tenax Co Ltd | Polyacrylonitrile-based carbon fiber and method for producing the same |
| CN103012790A (en) * | 2012-12-19 | 2013-04-03 | 成都德美精英化工有限公司 | Bisphthalonitrile-amino phenoxy phthalonitrile copolymer and condensate, and glass fiber composite material and preparation method thereof |
| CN103193977A (en) * | 2013-04-01 | 2013-07-10 | 河北工业大学 | Method for curing poly benzonitrile resin by amino phenoxy phthalonitrile |
| US20140039151A1 (en) * | 2012-08-02 | 2014-02-06 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Synthesis of and curing additives for phthalonitriles |
| CN105315469A (en) * | 2015-09-30 | 2016-02-10 | 中国人民解放军国防科学技术大学 | Silicon-nitrile-based hybrid resin and synthesizing method thereof |
| WO2016099667A1 (en) * | 2014-12-15 | 2016-06-23 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Controlling crosslinking density and processing parameters of phthalonitriles |
| CN106631893A (en) * | 2015-10-30 | 2017-05-10 | 中国人民解放军国防科学技术大学 | Animophenoxy phthalonitrile resin monomer and synthetic method thereof |
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-
2018
- 2018-04-26 CN CN201810383119.XA patent/CN108442122B/en active Active
Patent Citations (10)
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|---|---|---|---|---|
| US20080255287A1 (en) * | 2007-04-13 | 2008-10-16 | The Government Of The Us, As Represented By The Secrectary Of The Navy | Phosphine oxide containing phthalonitriles |
| US20090069484A1 (en) * | 2007-09-06 | 2009-03-12 | The Government Of The Us, As Represented By The Secretary Of The Navy | Aromatic ether and alkynyl containing phthalonitriles |
| JP2010229572A (en) * | 2009-03-26 | 2010-10-14 | Toho Tenax Co Ltd | Polyacrylonitrile-based carbon fiber and method for producing the same |
| US20140039151A1 (en) * | 2012-08-02 | 2014-02-06 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Synthesis of and curing additives for phthalonitriles |
| CN103012790A (en) * | 2012-12-19 | 2013-04-03 | 成都德美精英化工有限公司 | Bisphthalonitrile-amino phenoxy phthalonitrile copolymer and condensate, and glass fiber composite material and preparation method thereof |
| CN103193977A (en) * | 2013-04-01 | 2013-07-10 | 河北工业大学 | Method for curing poly benzonitrile resin by amino phenoxy phthalonitrile |
| WO2016099667A1 (en) * | 2014-12-15 | 2016-06-23 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Controlling crosslinking density and processing parameters of phthalonitriles |
| CN105315469A (en) * | 2015-09-30 | 2016-02-10 | 中国人民解放军国防科学技术大学 | Silicon-nitrile-based hybrid resin and synthesizing method thereof |
| CN106631893A (en) * | 2015-10-30 | 2017-05-10 | 中国人民解放军国防科学技术大学 | Animophenoxy phthalonitrile resin monomer and synthetic method thereof |
| CN106928488A (en) * | 2017-04-11 | 2017-07-07 | 大连理工大学 | Fabric enhancing blending resin base composite laminate of phthalonitrile containing Phthalazinone and preparation method thereof |
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| CN108442122B (en) | 2019-08-27 |
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