CN106751519B - A kind of glass fibre cage/epoxy resin composite material and preparation method thereof - Google Patents
A kind of glass fibre cage/epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN106751519B CN106751519B CN201611182956.3A CN201611182956A CN106751519B CN 106751519 B CN106751519 B CN 106751519B CN 201611182956 A CN201611182956 A CN 201611182956A CN 106751519 B CN106751519 B CN 106751519B
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- glass fibre
- cage
- epoxy resin
- composite material
- fibre cage
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a kind of glass fibre cage/epoxy resin composite materials and preparation method thereof, the composite material is using epoxy resin as matrix, using modified glass-fiber cage as reinforcement, wherein modified glass-fiber cage is the glass fibre cage of surface grafting dissaving polymer；The weight ratio of glass fibre cage and epoxy resin is 1:10~100.Preparation method includes the following steps: to carry out silanization treatment to glass fibre cage；Cladding dissaving polymer is impregnated on silanized glass fibre cage surface, obtains modified glass-fiber cage；Epoxy resin-base is poured into modified glass-fiber cage, solidifies, obtains glass fibre cage/epoxy resin composite material.Composite material of the invention is using modified glass-fiber cage as reinforcement, glass fibre cage shows excellent mechanical property, when composite material is acted on by plus load, glass fibre cage undertakes load effect, structural advantage is played, the physical and mechanical property and toughness of epoxy resin-base composite material can be greatly improved.
Description
Technical field
The present invention relates to a kind of epoxy resin-base composite materials and preparation method thereof, and in particular to and a kind of glass fibre cage/
Epoxy resin composite material and preparation method thereof.
Background technique
Epoxy resin (epoxy resin) refers to containing two or more epoxy groups, with aliphatic, alicyclic or fragrant
The organic compounds such as fragrant race are skeleton and can react the high-molecular oligomers body to form thermoset products by epoxy group, have liquid
The variforms such as state, sticky state, solid-state.Since epoxy resin has excellent processing performance, mechanical performance and physical property, institute
Manufactured coating, adhesive, composite resin matrix, electronic package material etc. are widely used in machinery, electronics, electric appliance, boat
The fields such as sky, space flight, chemical industry, communications and transportation, building.Although epoxy resin advantage is numerous, such as excellent mechanical property and heat are steady
It is qualitative, but since its curing system crosslink density is high, the internal stress generated in solidification process is not easy to eliminate, and causes curing system crisp
Property it is big, toughness is insufficient, limits application of the epoxy resin in various fields especially advanced material field.
Glass fibre is a kind of inorganic non-metallic material haveing excellent performance, many kinds of, and advantage is good insulating, heat resistance
By force, corrosion resistance is good, high mechanical strength.Glass fibre is used as to the modified material of epoxy resin, is greatly improved epoxy resin
Tensile strength, elasticity modulus, impact resistance, fatigue durability and fracture toughness, have extremely important application value.But
It is that there is presently no about glass fibre cage/epoxy resin composite material relevant report.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide a kind of glass fibre cage/epoxy resin composite material；This hair
Bright second is designed to provide glass fibre cage/epoxy resin composite material preparation method.
Technical solution: glass fibre cage/epoxy resin composite material of the invention, using epoxy resin as matrix, to change
Property glass fibre cage be reinforcement, the modified glass-fiber cage be surface grafting dissaving polymer glass fibre cage；Wherein,
In the glass fibre cage/epoxy resin composite material, the weight ratio of glass fibre cage and epoxy resin is 1:10~100.
Above-mentioned glass fibre cage can be multiple rule structure type, and preferably its section is triangle, square or positive six side
Shape, above-mentioned three kinds of shaping structures processing is convenient and easily places in composite molding；It can vertically and horizontally be handed over by glass fibre edge
It miscodes and knits, preferably longitudinally upper equidistant interval braiding, spacing distance are the 1/20~1/10 of glass fibre length；Preferably,
Selecting diameter is 30 μm, and length is the glass fibre of 100mm to weave；Preferably using E- glass fibre as knitted material.
The dissaving polymer for being grafted on glass fibre cage surface can be multiple types, and preferably amine-terminated hyperbrancedization polymerize
Object, epoxy terminated dissaving polymer, end phenolic group dissaving polymer or Hyperbranched Polymer with Terminal Hydroxyl.
Glass fibre cage/epoxy resin composite material preparation method of the invention includes the following steps:
(1) silanization treatment is carried out to the glass fibre cage of 1 parts by weight；
Specifically, can immerse 1 parts by weight of glass fiber cage in 40 parts by weight of toluene, 80 DEG C are warming up to, 0.5 weight is added
Part γ-aminopropyl triethoxysilane, reflux 4h, washing, 80 DEG C of vacuum drying 12h obtain silanized glass fibre cage.
(2) cladding dissaving polymer is impregnated on silanized glass fibre cage surface, obtains modified glass-fiber cage；
Preferably, silanized glass fibre cage made from step (1) can be added in 20 parts by weight dissaving polymers,
3~10h is impregnated at 60~110 DEG C, washing, drying obtain modified glass-fiber cage.
(3) 10~100 parts by weight epoxy resin matrixes are poured into modified glass-fiber cage, solidify, obtains glass fibers
Tie up cage/epoxy resin composite material.
Preferably, after epoxy resin-base being poured into modified glass-fiber cage, solidify 1 hour prior to 110 DEG C, then at
160 DEG C solidify 2 hours.Preferred amine curing agent in solidification process, amine curing agent are preferably 4,4'-diaminodiphenyl sulfone.
The utility model has the advantages that compared with prior art, remarkable advantage of the invention are as follows:
(1) glass fibre of the invention cage/epoxy resin composite material is a kind of novel epoxy resin-base composite material,
Using modified glass-fiber cage as reinforcement, glass fibre basket structure is unique, shows excellent mechanical property, works as glass fibre
When cage/epoxy resin composite material is acted on by plus load, glass fibre cage undertakes load effect, plays structural advantage, energy
Enough greatly improve the physical and mechanical property and toughness of epoxy resin-base composite material；
(2) silanization treatment first is carried out to glass fibre cage in preparation method of the invention, changes it between polymer
Compatibility；It reuses dissaving polymer and dipping cladding is carried out to its surface, there is glass fibre cage surface a large amount of living
Property group, with resin matrix in active group reactivity is high, compatibility is good, can be improved its boundary between resin matrix
Face caking property enhances interface binding intensity；Finally carry out moulding by casting, maintenance, gained glass fibre cage/epoxy resin composite wood
Material has excellent mechanical property.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the glass fibre cage that section is square；
Fig. 2 is the structural schematic diagram for the glass fibre cage that section is triangle；
Fig. 3 is the structural schematic diagram for the glass fibre cage that section is regular hexagon.
Specific embodiment
Technical solution of the present invention is described further with reference to the accompanying drawing.
Glass fibre cage/epoxy resin composite material of the invention, using epoxy resin as matrix, with modified glass-fiber cage
For reinforcement, which is the glass fibre cage of surface grafting dissaving polymer.
Wherein, glass fibre cage can be multiple rule structure type, cross sectional shape can be various polygons, as Fig. 1~
3, section is preferably triangle, square or regular hexagon.
Embodiment 1
Firstly, the glass fibre cage (such as Fig. 1) that the section 1g is triangle is immersed in 40g toluene, 80 DEG C are warming up to, dropwise
0.5g γ-aminopropyl triethoxysilane is added, flow back 4h, respectively three times using toluene and deionized water washing, 80 DEG C of vacuum
Dry 12h.Secondly, the addition of silanized glass fibre cage to be warming up to 60 DEG C of Hyperbranched Polymer with Terminal Amido (20g) in advance
In, impregnate 4h, three times using acetone washing, 80 DEG C of vacuum drying 12h.Finally, modified glass-fiber cage is placed in mold, note
Enter to be pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone mixture,
And solidify 1 hour in 110 DEG C, solidify 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.Measure it
Tensile strength, stretch modulus, impact strength, bending strength and bending modulus are respectively 50.67MPa, 2.34GPa, 44.87KJ/
m2, 96.56MPa and 2.56GPa.
Embodiment 2
Firstly, the glass fibre cage (such as Fig. 1) that the section 3g is triangle is immersed in 40g toluene, 80 DEG C are warming up to, dropwise
0.5g γ-aminopropyl triethoxysilane is added, flow back 4h, respectively three times using toluene and deionized water washing, 80 DEG C of vacuum
Dry 12h.Secondly, the addition of silanized glass fibre cage to be warming up to 80 DEG C of Hyperbranched Polymer with Terminal Amido (20g) in advance
In, impregnate 6h, three times using acetone washing, 80 DEG C of vacuum drying 12h.Finally, modified glass-fiber cage is placed in mold, note
Enter to be pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone mixture,
And solidify 1 hour in 110 DEG C, solidify 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.Measure it
Tensile strength, stretch modulus, impact strength, bending strength and bending modulus are respectively 61.54MPa, 2.56GPa, 48.43KJ/
m2, 98.78MPa and 2.78GPa.
Embodiment 3
Firstly, the glass fibre cage (such as Fig. 1) that the section 5g is triangle is immersed in 40g toluene, 80 DEG C are warming up to, dropwise
0.5g γ-aminopropyl triethoxysilane is added, flow back 4h, respectively three times using toluene and deionized water washing, 80 DEG C of vacuum
Dry 12h.Secondly, the addition of silanized glass fibre cage to be warming up to 80 DEG C of Hyperbranched Polymer with Terminal Amido (20g) in advance
In, impregnate 8h, three times using acetone washing, 80 DEG C of vacuum drying 12h.Finally, modified glass-fiber cage is placed in mold, note
Enter to be pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone mixture,
And solidify 1 hour in 110 DEG C, solidify 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.Measure it
Tensile strength, stretch modulus, impact strength, bending strength and bending modulus are respectively 60.76MPa, 2.49GPa, 46.12KJ/
m2, 90.23MPa and 2.64GPa.
Embodiment 4
Firstly, the glass fibre cage (such as Fig. 2) that the section 2g is square immerses in 40g toluene, 80 DEG C are warming up to, dropwise
0.5g γ-aminopropyl triethoxysilane is added, flow back 4h, respectively three times using toluene and deionized water washing, 80 DEG C of vacuum
Dry 12h.Secondly, the addition of silanized glass fibre cage to be warming up to 80 DEG C of epoxy terminated dissaving polymer in advance
In (20g), 3h, three times using acetone washing, 80 DEG C of vacuum drying 12h are impregnated.Finally, modified glass-fiber cage is placed in mold
In, injection is pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone is mixed
Object is closed, and is solidified 1 hour in 110 DEG C, solidifies 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.It surveys
Measure its tensile strength, stretch modulus, impact strength, bending strength and bending modulus be respectively 56.48MPa, 2.28GPa,
43.86KJ/m2, 88.43MPa and 2.47GPa.
Embodiment 5
Firstly, the glass fibre cage (such as Fig. 2) that the section 4g is square immerses in 40g toluene, 80 DEG C are warming up to, dropwise
0.5g γ-aminopropyl triethoxysilane is added, flow back 4h, respectively three times using toluene and deionized water washing, 80 DEG C of vacuum
Dry 12h.Secondly, the addition of silanized glass fibre cage to be warming up to 110 DEG C of epoxy terminated dissaving polymer in advance
In (20g), 6h, three times using acetone washing, 80 DEG C of vacuum drying 12h are impregnated.Finally, modified glass-fiber cage is placed in mold
In, injection is pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone is mixed
Object is closed, and is solidified 1 hour in 110 DEG C, solidifies 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.It surveys
Measure its tensile strength, stretch modulus, impact strength, bending strength and bending modulus be respectively 32.54MPa, 1.74GPa,
30.25KJ/m2, 78.67MPa and 2.13GPa.
Embodiment 6
Firstly, the glass fibre cage (such as Fig. 2) that the section 6g is square immerses in 40g toluene, 80 DEG C are warming up to, dropwise
0.5g γ-aminopropyl triethoxysilane is added, flow back 4h, respectively three times using toluene and deionized water washing, 80 DEG C of vacuum
Dry 12h.Secondly, the addition of silanized glass fibre cage to be warming up to 80 DEG C of epoxy terminated dissaving polymer in advance
In (20g), 10h, three times using acetone washing, 80 DEG C of vacuum drying 12h are impregnated.Finally, modified glass-fiber cage is placed in mould
In tool, injection is pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone
Mixture, and solidify 1 hour in 110 DEG C, solidify 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.
Measure its tensile strength, stretch modulus, impact strength, bending strength and bending modulus be respectively 59.25MPa, 2.29GPa,
44.22KJ/m2, 84.98MPa and 2.51GPa.
Embodiment 7
Firstly, the section 3g is positive in hexagonal glass fibre cage (such as Fig. 3) immersion 40g toluene, 80 DEG C are warming up to, by
It is added dropwise to 0.5g γ-aminopropyl triethoxysilane, flow back 4h, and respectively three times using toluene and deionized water washing, 80 DEG C true
The dry 12h of sky.Secondly, the addition of silanized glass fibre cage to be warming up to 80 DEG C of end phenolic group dissaving polymer in advance
In (20g), 6h, three times using acetone washing, 80 DEG C of vacuum drying 12h are impregnated.Finally, modified glass-fiber cage is placed in mold
In, injection is pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone is mixed
Object is closed, and is solidified 1 hour in 110 DEG C, solidifies 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.It surveys
Measure its tensile strength, stretch modulus, impact strength, bending strength and bending modulus be respectively 58.54MPa, 2.37GPa,
45.26KJ/m2, 92.34MPa and 2.56GPa.
Embodiment 8
Firstly, the section 6g is positive in hexagonal glass fibre cage (such as Fig. 3) immersion 40g toluene, 80 DEG C are warming up to, by
It is added dropwise to 0.5g γ-aminopropyl triethoxysilane, flow back 4h, and respectively three times using toluene and deionized water washing, 80 DEG C true
The dry 12h of sky.Secondly, the addition of silanized glass fibre cage to be warming up to 80 DEG C of Hyperbranched Polymer with Terminal Hydroxyl in advance
In (20g), 6h, three times using acetone washing, 80 DEG C of vacuum drying 12h are impregnated.Finally, modified glass-fiber cage is placed in mold
In, injection is pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone is mixed
Object is closed, and is solidified 1 hour in 110 DEG C, solidifies 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.It surveys
Measure its tensile strength, stretch modulus, impact strength, bending strength and bending modulus be respectively 56.14MPa, 2.25GPa,
42.74KJ/m2, 87.43MPa and 2.32GPa.
Embodiment 9
Firstly, the section 10g is positive in hexagonal glass fibre cage (such as Fig. 3) immersion 40g toluene, 80 DEG C are warming up to,
0.5g γ-aminopropyl triethoxysilane is added dropwise, flow back 4h, respectively three times using toluene and deionized water washing, 80 DEG C
It is dried in vacuo 12h.Secondly, the addition of silanized glass fibre cage to be warming up to 80 DEG C of Hyperbranched Polymer with Terminal Hydroxyl in advance
In (20g), 10h, three times using acetone washing, 80 DEG C of vacuum drying 12h are impregnated.Finally, modified glass-fiber cage is placed in mould
In tool, injection is pre-mixed uniform 100g bisphenol A-type diglycidyl ether epoxy resin and 35g 4,4'-diaminodiphenyl sulfone
Mixture, and solidify 1 hour in 110 DEG C, solidify 2 hours then at 160 DEG C, obtains glass fibre cage/epoxy resin composite material.
Measure its tensile strength, stretch modulus, impact strength, bending strength and bending modulus be respectively 60.76MPa, 2.54GPa,
47.25KJ/m2, 94.67MPa and 2.57GPa.
Claims (9)
1. a kind of glass fibre cage/epoxy resin composite material, which is characterized in that the glass fibre cage/epoxy resin composite wood
Material is using epoxy resin as matrix, and using modified glass-fiber cage as reinforcement, which is that surface grafting is hyperbranched
The glass fibre cage of polymer；In the glass fibre cage/epoxy resin composite material, the weight of glass fibre cage and epoxy resin
Amount is than being 1:10~100；
The preparation method of the glass fibre cage/epoxy resin composite material includes the following steps:
(1) silanization treatment is carried out to the glass fibre cage of 1 parts by weight；
(2) cladding dissaving polymer is impregnated on silanized glass fibre cage surface, obtains modified glass-fiber cage；
(3) 10~100 parts by weight epoxy resin matrixes are poured into modified glass-fiber cage, solidify, obtain glass fibre cage/
Epoxy resin composite material.
2. glass fibre cage/epoxy resin composite material according to claim 1, which is characterized in that the glass fibre
The section of cage is triangle, square or regular hexagon.
3. glass fibre cage/epoxy resin composite material according to claim 1, which is characterized in that the glass fibre
Cage is formed by glass fibre along vertically and horizontally weaving, and the diameter of the glass fibre is 30 μm, length 100mm.
4. glass fibre cage/epoxy resin composite material according to claim 3, which is characterized in that the glass fibre
Equidistant interval weaves along longitudinal direction, and spacing distance is the 1/20~1/10 of glass fibre length.
5. glass fibre cage/epoxy resin composite material according to claim 1, which is characterized in that the hyperbranched poly
Conjunction object is Hyperbranched Polymer with Terminal Amido, epoxy terminated dissaving polymer, end phenolic group dissaving polymer or terminal hydroxy group over-expense
Fluidized polymer.
6. glass fibre cage/epoxy resin composite material according to claim 1, which is characterized in that in step (1), by 1
Parts by weight of glass fiber cage immerses in 40 parts by weight of toluene, is warming up to 80 DEG C, and 0.5 parts by weight γ-aminopropyl-triethoxy is added
Silane, reflux 4h, washing, 80 DEG C of vacuum drying 12h obtain silanized glass fibre cage.
7. glass fibre cage/epoxy resin composite material according to claim 1, which is characterized in that, will in step (2)
Silanized glass fibre cage made from step (1) be added 20 parts by weight dissaving polymers in, at 60~110 DEG C impregnate 3~
10h, washing, drying, obtains modified glass-fiber cage.
8. glass fibre cage/epoxy resin composite material according to claim 1, which is characterized in that in step (3), Gu
Change condition is to solidify 1 hour prior to 110 DEG C, is solidified 2 hours then at 160 DEG C.
9. glass fibre cage/epoxy resin composite material according to claim 1, which is characterized in that in step (3), Gu
The curing agent used during changing is amine curing agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611182956.3A CN106751519B (en) | 2016-12-20 | 2016-12-20 | A kind of glass fibre cage/epoxy resin composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611182956.3A CN106751519B (en) | 2016-12-20 | 2016-12-20 | A kind of glass fibre cage/epoxy resin composite material and preparation method thereof |
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| CN106751519B true CN106751519B (en) | 2019-01-22 |
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| CN114405157B (en) * | 2021-12-27 | 2023-07-14 | 重庆再升科技股份有限公司 | High-strength fluid separation medium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55149162A (en) * | 1979-05-09 | 1980-11-20 | Kurimoto Ltd | Manufacture of glass long fiber reinforcing basket |
| CN105293955A (en) * | 2015-12-03 | 2016-02-03 | 盐城工学院 | Glass fibre modification method and application thereof |
| CN105315475A (en) * | 2014-07-16 | 2016-02-10 | 合复新材料科技(无锡)有限公司 | Fiber reinforced resin composite material, preparation method and applications thereof |
-
2016
- 2016-12-20 CN CN201611182956.3A patent/CN106751519B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55149162A (en) * | 1979-05-09 | 1980-11-20 | Kurimoto Ltd | Manufacture of glass long fiber reinforcing basket |
| CN105315475A (en) * | 2014-07-16 | 2016-02-10 | 合复新材料科技(无锡)有限公司 | Fiber reinforced resin composite material, preparation method and applications thereof |
| CN105293955A (en) * | 2015-12-03 | 2016-02-03 | 盐城工学院 | Glass fibre modification method and application thereof |
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