CN110128787A - A kind of glass fiber reinforced plastics composite material and preparation method thereof - Google Patents
A kind of glass fiber reinforced plastics composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/49—Phosphorus-containing compounds
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- 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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Abstract
The invention discloses a kind of glass fiber reinforced plastics composite materials, according to parts by weight, the glass fiber reinforced plastics composite material includes following component: 60~70 parts of epoxy resin, 20~30 parts of furane resins, 3~5 parts of filler, 1~3 part of curing agent, 1~3 part of promotor, 20~30 parts of glass fibre, 3~6 parts of sodium citrate, 5~10 parts of magnesium nitrate, 2~5 parts of citric acid, 1~3 part of aluminium hydroxide；The glass fiber reinforced plastics composite material has good high temperature resistance and good flame retardation effect.
Description
Technical field
The present invention relates to polymer composite manufacturing field more particularly to a kind of glass fiber reinforced plastics composite material and its preparation sides
Method.
Background technique
Composite material is by two or more independent physics phases, including adhesives (matrix) and pellet, fiber
Or a kind of solid product composed by flaky material.Composite material is at least combined by two or more ingredients, these ingredients one
It works, keeps the characteristic of composite material and component totally different.Most of composite material is made of basis material and reinforcing material,
Matrix constitutes composite continuous phase, and reinforcing material improves the strength and stiffness of matrix, and reinforcing material is usually in fiber state.Now
Common artificial compounded material can be divided into three categories (by substrate types point):
(1) polymer composites (PMC): using polymer for matrix, and glass fibre, carbon fiber, aramid fiber are to increase
Strong material.Glass reinforced plastic/composite material is as such.
(2) metal-base composites (MMC): being enhancing with fiber (such as silicon carbide fibre) with metal (such as aluminium) for matrix
Material has application on automobile.
(3) inorganic non-metallic based composites (CMC): using ceramics as matrix, with staple fiber or whisker (such as silicon carbide and carbon
Change boron fibre or whisker) enhancing ceramic matric composite, using carbon fiber as reinforcing material, and it is compound as carbon/carbon of matrix using carbon
Material etc..
Glass fiber reinforced plastics composite material is commonly called as glass reinforced plastic in China, is the maximum composite material of current dosage, accounts for Modern Significance
90% or more of composite material yield.The existing usual high temperature resistance of glass fiber reinforced plastics composite material is poor.With low-carbon economy society
The arriving of meeting, the application field of glass-reinforced plastic material expand constantly, and the high temperature resistance of glass fiber reinforced plastics composite material is wanted in market
Ask higher and higher.Therefore, it is badly in need of the new glass fiber reinforced plastics composite material of one kind in industry at present to solve to ask present in the prior art
Topic.
Summary of the invention
It is an object of the invention to overcome the defect of the prior art, a kind of glass fiber reinforced plastics composite material and its preparation side are provided
Method, the glass fiber reinforced plastics composite material have good high temperature resistance and good flame retardation effect.
The present invention is implemented as follows:
It is an object of the present invention to provide a kind of glass fiber reinforced plastics composite materials, and according to parts by weight, the glass reinforced plastic is compound
Material includes following component: according to parts by weight, the glass fiber reinforced plastics composite material includes following component: epoxy resin 60~70
Part, 20~30 parts of furane resins, 3~5 parts of filler, 1~3 part of curing agent, 1~3 part of promotor, 20~30 parts of glass fibre, lemon
3~6 parts of lemon acid sodium, 5~10 parts of magnesium nitrate, 2~5 parts of citric acid, 1~3 part of aluminium hydroxide.
The second object of the present invention is to provide the preparation method of glass fiber reinforced plastics composite material described in one kind, the method packet
Include following steps:
Step 1, by 20~30 parts of 60~70 parts of epoxy resin, furane resins investment reaction kettles, be heated to 60 DEG C
~80 DEG C of reaction 3h~5h, obtain component A after fully reacting；
Step 2, by 3~5 parts of filler, 1~3 part of curing agent, 1~3 part of promotor, 3~6 parts of sodium citrate, magnesium nitrate 5~
10 parts, 2~5 parts of citric acid, 1~3 part of aluminium hydroxide be sufficiently mixed and adjust PH to 2~5, obtain B component；
Step 3 is presoaked in the open, component A, B component are mixed and are added 20~30 parts of glass fibre, is done
The glass fiber reinforced plastics composite material is prepared in dry and processing.
Compared with prior art, the invention has the advantages that and effect:
A kind of glass fiber reinforced plastics composite material provided by the invention with good high temperature resistance, good flame retardation effect, has more
Strong corrosion resistance, specifically:
(1) magnesium ion that magnesium nitrate ionizes out and the OH at citric acid ionization-Generate a small amount of magnesium hydroxide, magnesium hydroxide
For inorganic fire retardants and noxious material is free of, it is environmentally friendly；Magnesium hydroxide also has the function of that cigarette is inhibited to generate simultaneously, so that
The flame retardant property of the glass fiber reinforced plastics composite material is more preferably；Magnesium hydroxide can also effectively improve the corrosion-resistant of the glass fiber reinforced plastics composite material
Property, to increase the service life of the glass fiber reinforced plastics composite material.
(2) with sodium citrate the chelate (lemon that metathesis reaction generates a similar cross-linked network occurs for magnesium nitrate
Lemon acid magnesium), magnesium and carboxyl are ionic bonds, and chelate is coordinate bond, and what is utilized is the lone pair electrons and metal ion on carboxyl
The effect of unoccupied orbital.Chelate effectively avoids the generation of free radical, so can effectively change the high temperature resistance of the composite material.
(3) aluminium hydroxide is to integrate fire-retardant, suppression cigarette, the fire retardant for filling three zones, nontoxic, corrosion-free, stable
Toxic gas is not generated under the good, high temperature of property, and cheap, it is from a wealth of sources.Magnesium hydroxide decomposes between 340 DEG C~490 DEG C.
Thermal stability is good, has good fire-retardant and smoke effect, particularly suitable for the higher polyolefin plastics of processing temperature.Hydroxide
Both aluminium and magnesium hydroxide compound use can be complementary to one another, and flame retardant property is got well than effect is used alone.
(4) triphenylphosphine as promotor while have the effect of fire-retardant, further increase glass fiber reinforced plastics composite material
Flame retardant property.
(5) other materials (including glass fibre) is adhesively-bonded together to form by epoxy resin and furane resins as adhesive
The organic and hybrid cross-linked three-dimensional network stereochemical structure of inorganic material, crosslink density is high, and the chelate effectively avoids dissociating
The generation of base, thus there is extremely strong corrosion resistance.
Specific embodiment
Embodiment 1
The present embodiment provides a kind of glass fiber reinforced plastics composite materials according to parts by weight, including following component: 65 parts of epoxy resin,
25 parts of furane resins, 4 parts of filler, 2 parts of curing agent, 2 parts of promotor, 25 parts of glass fibre, 4 parts of sodium citrate, 8 parts of magnesium nitrate,
3 parts of citric acid, 2 parts of aluminium hydroxide.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps:
Step 1 is put into epoxy resin, furane resins in reaction kettle by the proportion, is heated to 60 DEG C~80 DEG C
3h~5h is reacted, obtains component A after fully reacting；
Filler, curing agent, promotor, sodium citrate, magnesium nitrate, citric acid, aluminium hydroxide are pressed the proportion by step 2
It is sufficiently mixed and is adjusted PH to 3, obtains B component；
In the open, component A, B component are being mixed and presoaked by proportion addition glass fibre for step 3,
It dries and processes and the glass fiber reinforced plastics composite material is prepared.
Embodiment 2
The present embodiment provides a kind of glass fiber reinforced plastics composite materials according to parts by weight, including following component: 60 parts of epoxy resin,
20 parts of furane resins, 3 parts of filler, 1 part of curing agent, 3 parts of promotor, 30 parts of glass fibre, 6 parts of sodium citrate, 5 parts of magnesium nitrate,
2 parts of citric acid, 1 part of aluminium hydroxide.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps:
Step 1 is put into epoxy resin, furane resins in reaction kettle by the proportion, is heated to 60 DEG C~80 DEG C
3h~5h is reacted, obtains component A after fully reacting；
Filler, curing agent, promotor, sodium citrate, magnesium nitrate, citric acid, aluminium hydroxide are pressed the proportion by step 2
It is sufficiently mixed and is adjusted PH to 2, obtains B component；
In the open, component A, B component are being mixed and presoaked by proportion addition glass fibre for step 3,
It dries and processes and the glass fiber reinforced plastics composite material is prepared.
Embodiment 3
The present embodiment provides a kind of glass fiber reinforced plastics composite materials according to parts by weight, including following component: 70 parts of epoxy resin,
30 parts of furane resins, 5 parts of filler, 3 parts of curing agent, 1 part of promotor, 20 parts of glass fibre, 3 parts of sodium citrate, 10 parts of magnesium nitrate,
5 parts of citric acid, 3 parts of aluminium hydroxide.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps:
Step 1 is put into epoxy resin, furane resins in reaction kettle by the proportion, is heated to 60 DEG C~80 DEG C
3h~5h is reacted, obtains component A after fully reacting；
Filler, curing agent, promotor, sodium citrate, magnesium nitrate, citric acid, aluminium hydroxide are pressed the proportion by step 2
It is sufficiently mixed and is adjusted PH to 4, obtains B component；
In the open, component A, B component are being mixed and presoaked by proportion addition glass fibre for step 3,
It dries and processes and the glass fiber reinforced plastics composite material is prepared.
Embodiment 4
The present embodiment provides a kind of glass fiber reinforced plastics composite materials according to parts by weight, including following component: 68 parts of epoxy resin,
26 parts of furane resins, 4 parts of filler, 2 parts of curing agent, 2 parts of promotor, 26 parts of glass fibre, 5 parts of sodium citrate, 8 parts of magnesium nitrate,
5 parts of citric acid, 3 parts of aluminium hydroxide.
The preparation method of the glass fiber reinforced plastics composite material includes the following steps:
Step 1 is put into epoxy resin, furane resins in reaction kettle by the proportion, is heated to 60 DEG C~80 DEG C
3h~5h is reacted, obtains component A after fully reacting；
Filler, curing agent, promotor, sodium citrate, magnesium nitrate, citric acid, aluminium hydroxide are pressed the proportion by step 2
It is sufficiently mixed and is adjusted PH to 5, obtains B component；
In the open, component A, B component are being mixed and presoaked by proportion addition glass fibre for step 3,
It dries and processes and the glass fiber reinforced plastics composite material is prepared.
Comparative example 1
For the comparative example in addition to sodium citrate, magnesium nitrate, citric acid is not added, remaining component, content and preparation method are same
Embodiment 1.
Comparative example 2
For the comparative example in addition to sodium citrate, magnesium nitrate, citric acid is not added, remaining component, content and preparation method are same
Embodiment 2.
Comparative example 3
For the comparative example in addition to sodium citrate, magnesium nitrate, citric acid is not added, remaining component, content and preparation method are same
Embodiment 3.
Comparative example 4
For the comparative example in addition to sodium citrate, magnesium nitrate, citric acid is not added, remaining component, content and preparation method are same
Embodiment 4.
The measurement of 1 correlated performance of experimental example
Glass fiber reinforced plastics composite material made from above-described embodiment and comparative example is tested for the property, performance such as table 1, table 2
It is shown.
1, test method is as follows:
(1) test condition of heat distortion temperature are as follows: GB/T 5989-2008 is just compound to polyester fiberglass according to national standards
The heat distortion temperature of material is tested.
(2) oxygen index (OI): fibre reinforced plastics combustibility test method oxygen index method GB/T8924-2005.
(8) heat resistance of glass fiber reinforced plastics composite material, the change of hardness and degree of drawing corrosion resistance: are probed under salt etching condition
Change.
2, test result
(1) it detects embodiment 1- embodiment 3 and the heat distortion temperature and oxygen index (OI) of comparative example 1-3 is as shown in table 1.
Table 1
| Project | Heat distortion temperature (DEG C) | Oxygen index (OI) (%) |
| Embodiment 1 | 176 | 94 |
| Comparative example 1 | 112 | 63 |
| Embodiment 2 | 169 | 89 |
| Comparative example 2 | 105 | 58 |
| Embodiment 3 | 167 | 86 |
| Comparative example 3 | 103 | 59 |
| Embodiment 4 | 152 | 81 |
| Comparative example 4 | 97 | 46 |
As shown in Table 1, compared to comparative example 1-4, the oxygen index (OI) of embodiment 1-4 belongs to non-ignitable product, has 70% or more
Good anti-flammability.
Compared to comparative example 1-4, a certain amount of magnesium nitrate of the addition of embodiment 1-4, sodium citrate, citric acid can be effective
Raising the fiber glass epoxy heat distortion temperature, heat distortion temperature is higher, and its high temperature resistance of explanation is better.
(2) after corroding 60 days (etching condition: salinity 3%, temperature are 50 DEG C), corrosion front and back hardness test is compared.
Hardness test was widely used hardness Barcol using modern age in the world and is tested.Test method refers to GB/T3854-
2005 fibre reinforced plastics hardness Barcol test methods are tested.Carrying out surface hardness for glass fiber reinforced plastics composite material is more than 50
When each sample survey 10 points；When glass fiber reinforced plastics composite material carries out surface hardness lower than 50, each sample surveys 20 points, takes arithmetic
Average value is as sample hardness value.Hardness Barcol retains percentage (A) and is calculated with following formula: A=(H/H0) × 100%；In formula, H
For the hardness Barcol of sample after corrosion；H0For the hardness Barcol for corroding preceding sample.
Table 2
| Project | Hardness before corrosion | Hardness after corrosion | Retention rate (%) |
| Embodiment 1 | 95 | 82 | 86.3 |
| Comparative example 1 | 82 | 54 | 65.8 |
| Embodiment 2 | 91 | 78 | 85.7 |
| Comparative example 2 | 79 | 51 | 64.6 |
| Embodiment 3 | 89 | 75 | 84.3 |
| Comparative example 3 | 78 | 45 | 57.7 |
| Embodiment 4 | 85 | 71 | 83.5 |
| Comparative example 4 | 81 | 42 | 51.8 |
After (3) 60 days (etching condition: salinity 3%, temperature are 50 DEG C), corrosion front and back tensile strength is compared.
Tensile strength refers to the maximum stress that material is born before tension failure, when maximum stress occurs in fracture
Referred to as fracture tensile strength.
Table 3
| Project | Tensile strength (Mpa) before corrosion | Tensile strength (Mpa) after corrosion |
| Embodiment 1 | 96 | 71 |
| Comparative example 1 | 82 | 35 |
| Embodiment 2 | 91 | 68 |
| Comparative example 2 | 84 | 39 |
| Embodiment 3 | 93 | 65 |
| Comparative example 3 | 81 | 26 |
| Embodiment 4 | 88 | 64 |
| Comparative example 4 | 76 | 23 |
By table 2, table 3 it is found that compared to comparative example 1-3, the glass fiber reinforced plastics composite material of embodiment 1-3 has extremely strong anti-corruption
Corrosion.
In conclusion a kind of glass fiber reinforced plastics composite material provided by the invention, has good high temperature resistance, flame retardant effect
Well, there is stronger corrosion resistance.
Experimental example 2
Prepare 6 parts of embodiments 1 and provides a kind of glass fiber reinforced plastics composite material (according to parts by weight, including following component: asphalt mixtures modified by epoxy resin
65 parts of rouge, 25 parts of furane resins, 4 parts of filler, 2 parts of curing agent, 2 parts of promotor, 25 parts of glass fibre, 4 parts of sodium citrate, nitric acid
8 parts of magnesium, 3 parts of citric acid, 2 parts of aluminium hydroxide), it is divided into 6 experimental groups, being adjusted to pH respectively is 1,2,3,4,5,6, test experience group
The heat distortion temperature and oxygen index (OI) of 1-6 is as shown in table 4.
Table 4
As shown in Table 4, pH value is affected to heat distortion temperature and oxygen index (OI), when prescription is the same, thermal change when pH=3
Shape temperature and oxygen index (OI) highest.
Described is only presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on should all include within protection scope of the present invention.
Claims (6)
1. a kind of glass fiber reinforced plastics composite material, which is characterized in that according to parts by weight, the glass fiber reinforced plastics composite material includes such as the following group
Part: 60~70 parts of epoxy resin, 20~30 parts of furane resins, 3~5 parts of filler, 1~3 part of curing agent, 1~3 part of promotor, glass
20~30 parts of glass fiber, 3~6 parts of sodium citrate, 5~10 parts of magnesium nitrate, 2~5 parts of citric acid, 1~3 part of aluminium hydroxide.
2. glass fiber reinforced plastics composite material as described in claim 1, which is characterized in that according to parts by weight, the glass reinforced plastic is compound
Material includes following component: 65 parts of epoxy resin, 25 parts of furane resins, 4 parts of filler, 2 parts of curing agent, 2 parts of promotor, glass fibers
Tie up 25 parts, 4 parts of sodium citrate, 8 parts of magnesium nitrate, 3 parts of citric acid, 2 parts of aluminium hydroxide.
3. glass fiber reinforced plastics composite material as described in claim 1, which is characterized in that the filler includes iron powder, copper powder, nano-sized carbon
At least one of sour calcium, the filler fineness are 300~500 mesh；
4. glass fiber reinforced plastics composite material as described in claim 1, which is characterized in that the curing agent is tetraethylenepentamine.
5. glass fiber reinforced plastics composite material as described in claim 1, which is characterized in that the promotor is triphenylphosphine.
6. a kind of preparation method of glass fiber reinforced plastics composite material as claimed in claims 1-5, which is characterized in that the preparation method
Include the following steps:
Step 1, by 20~30 parts of 60~70 parts of epoxy resin, furane resins investment reaction kettles, be heated to 60 DEG C~80
DEG C reaction 3h~5h, obtain component A after fully reacting；
Step 2, by 3~5 parts of filler, 1~3 part of curing agent, 1~3 part of promotor, 3~6 parts of sodium citrate, magnesium nitrate 5~10
Part, 2~5 parts of citric acid, 1~3 part of aluminium hydroxide be sufficiently mixed and adjust PH to 2~5, obtain B component；
Step 3 is presoaked in the open, component A, B component are mixed and are added 20~30 parts of glass fibre, it is dry simultaneously
The glass fiber reinforced plastics composite material is prepared in processing.
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| CN113248856A (en) * | 2021-05-25 | 2021-08-13 | 广州市华英防腐设备有限公司 | Composite glass fiber reinforced plastic and preparation method thereof |
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| CN107903827A (en) * | 2017-11-10 | 2018-04-13 | 雷笑天 | A kind of preparation method of high-adhesion high temperature resistant anchoring adhesive |
| CN107828312A (en) * | 2017-12-01 | 2018-03-23 | 武汉博奇玉宇环保股份有限公司 | Anti-flaming glass fiber reinforced plastics composite coating and preparation method thereof |
| CN107868574A (en) * | 2017-12-01 | 2018-04-03 | 武汉博奇玉宇环保股份有限公司 | Antisepsis composite material coating and preparation method thereof |
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Application publication date: 20190816 |