CN108442122B - Sizing agent for preparing quartz fiber/nitrile resin composite material - Google Patents
Sizing agent for preparing quartz fiber/nitrile resin composite material Download PDFInfo
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- CN108442122B CN108442122B CN201810383119.XA CN201810383119A CN108442122B CN 108442122 B CN108442122 B CN 108442122B CN 201810383119 A CN201810383119 A CN 201810383119A CN 108442122 B CN108442122 B CN 108442122B
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- Prior art keywords
- composite material
- sizing agent
- nitrile
- resin
- quartz fibre
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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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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 preparation and applied technical field, be related to one kind be used to prepare quartz fibre/
The sizing agent of Nitrile resin composite material.
Background technique
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 in domestic and international wave-penetrating composite material using most reinforcing fibers.When preparing electromagnetic wave transparent material, with the liter of temperature
Height, elasticity modulus are increase accordingly, accordingly ensure that electromagnetic wave transparent material, while wave transmission rate with higher, 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 is in contact the transition zone of composition with enhancing in composite material, and 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, includes 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 transmitting.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.
Summary of the invention
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 provides a kind of and quartz fibre/Nitrile resin composite material adaptation and 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 be used to prepare quartz fibre/Nitrile resin composite material sizing agent, it is wrapped
Coupling agent, cyano resin, catalyst and organic solvent are included,
Further, above-mentioned coupling agent is the silicon oxygen 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 silicon oxygen chain structure of phthalonitrile side chain；N is the silicon oxygen 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 of 4 kinds of chemicals represented by II-formula of formula V or a variety of mixing
Object:
Further, above-mentioned catalyst is 4- amino phenoxy phthalonitrile resin.
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 it is used to prepare quartz fibre/Nitrile resin composite material sizing agent the present invention provides a kind of,
The mass fraction of formula composition and each component are as follows:
It is highly preferred that it is used to prepare quartz fibre/Nitrile resin composite material sizing agent the present invention provides a kind of,
The mass fraction of formula composition and each component are as follows:
The invention sizing agent the preparation method is as follows: weighing coupling agent according to required proportion, cyano resin, catalyst, having
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 invention has the following advantages that
The present invention provides the sizing agents that this advanced composite material (ACM) of quartz fibre/cyano resin is applicable in；The coupling used
Agent one end is silicon oxygen chain, can be in conjunction 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, to play the bridge connection function on the two surface, 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 the binding performance between the quartz fibre and cyano resin interface can be improved, thus
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.
Detailed description of the invention
From the detailed description with reference to the accompanying drawing 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, in which:
Quartz fibre/Nitrile resin composite material sizing agent that is used to prepare of Fig. 1 preferred embodiment of the present invention preparation is consolidated
The DMA figure of solidfied material after change.
Specific embodiment
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 appended drawing reference 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 to be used to prepare quartz fibre/Nitrile resin composite material sizing agent, 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 configure by the component in embodiment 1 in addition to the solvents, the DMA figure of gained solidfied material, Cong Tuzhong after being heating and curing
It can be seen that the glass transition temperature of the solidfied material is 410 DEG C much higher than various sizing agents, the 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 of agent formula and the composite material of quartz textile preparation is 30MPa, 400 DEG C nearly higher than 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 to be used to prepare quartz fibre/Nitrile resin composite material sizing agent, 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, much higher than 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, 400 DEG C nearly higher than temperature tolerance of fire resistant resin quartz fibre composite material
Interlaminar shear strength illustrates that the sizing agent and quartz fibre have excellent interfacial combined function.
As can be seen that present inventor after series of studies, proposes 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 as limitation, 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 are obvious for those of ordinary skill.Therefore, protection scope of the present invention should be with right
It is required that protection scope subject to.
Claims (8)
1. a kind of be used to prepare quartz fibre/Nitrile resin composite material sizing agent, which is characterized in that it include coupling agent,
Cyano resin, catalyst and organic solvent；
The coupling agent is the silicon oxygen chain polymerization object with general formula shown in formula I:
In formula: m is the number of iterations of the silicon oxygen chain structure of phthalonitrile side chain；N is the silicon oxygen chain structure containing thiol side chain
Number of iterations.
2. being used to prepare quartz fibre/Nitrile resin composite material sizing agent as described in claim 1, 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.
3. being used to prepare quartz fibre/Nitrile resin composite material sizing agent as claimed in claim 2, which is characterized in that
The cyano resin is one of 4 kinds of chemicals represented by II-formula of formula V or a variety of mixtures:
4. being used to prepare quartz fibre/Nitrile resin composite material sizing agent as claimed in claim 3, which is characterized in that
The catalyst is 4- amino phenoxy phthalonitrile resin.
5. being used to prepare quartz fibre/Nitrile resin composite material sizing agent as claimed in claim 4, which is characterized in that
The organic solvent is one of acetone, tetrahydrofuran, DMF, ethyl acetate, butanone or a variety of.
6. being used to prepare quartz fibre/Nitrile resin composite material sizing agent as claimed in claim 5, which is characterized in that
The coupling agent, cyano resin, catalyst and organic solvent mass ratio be 5~20:5~30:5~20:100.
7. being used to prepare quartz fibre/Nitrile resin composite material sizing agent as claimed in claim 6, which is characterized in that
The mass fraction of its formula composition and each component are as follows:
8. being used to prepare quartz fibre/Nitrile resin composite material sizing agent as claimed in claim 6, which is characterized in that
The mass fraction of its formula composition and each component are as follows:
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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| Publication Number | Publication Date |
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| CN108442122A CN108442122A (en) | 2018-08-24 |
| CN108442122B true CN108442122B (en) | 2019-08-27 |
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Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US8039576B2 (en) * | 2007-09-06 | 2011-10-18 | The United States Of America As Represented By The Secretary Of The Navy | Aromatic ether and alkynyl containing phthalonitriles |
| JP5455408B2 (en) * | 2009-03-26 | 2014-03-26 | 東邦テナックス株式会社 | Polyacrylonitrile-based carbon fiber and method for producing the same |
| WO2014021946A1 (en) * | 2012-08-02 | 2014-02-06 | The Gov. Of The U.S. Of America As Represented By The Secretary Of The Navy | Synthesis of and curing additives for phthalonitriles |
| CN103012790B (en) * | 2012-12-19 | 2014-11-19 | 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 |
| US9464170B2 (en) * | 2014-12-15 | 2016-10-11 | The United States Of America, As Represented By The Secretary Of The Navy | Controlling crosslinking density and processing parameters of phthalonitriles |
| CN105315469B (en) * | 2015-09-30 | 2018-04-13 | 中国人民解放军国防科学技术大学 | Silicon substrate itrile group hybrid resin and its synthetic method |
| 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 |
| CN106928488B (en) * | 2017-04-11 | 2018-10-16 | 大连理工大学 | Fabric enhances blending resin base composite laminate of phthalonitrile containing Phthalazinone and preparation method thereof |
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