CN109517354A - A kind of fire-retardant resistance to compression composite material and preparation method for glass toughening manure pit - Google Patents
A kind of fire-retardant resistance to compression composite material and preparation method for glass toughening manure pit Download PDFInfo
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- CN109517354A CN109517354A CN201811398510.3A CN201811398510A CN109517354A CN 109517354 A CN109517354 A CN 109517354A CN 201811398510 A CN201811398510 A CN 201811398510A CN 109517354 A CN109517354 A CN 109517354A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a kind of fire-retardant resistance to compression composite material and preparation methods for glass toughening manure pit, it is related to glass fibre reinforced plastics technology field, raw material includes: 100 parts of unsaturated polyester resin, 3-7 parts of acrylonitrile-butadiene-styrene copolymer, 80-110 parts of glass fibre, 3-7 parts of silicon powder, 20-30 parts of bentonite, 6-12 parts of epoxy propane butyl ether, 3-7 parts of curing agent, 2-5 parts of promotor, 2-5 parts of fire retardant, 0.5-2 parts of benzotriazole, 0.5-2 parts of butyl benzyl phthalate, 1-3 parts of coupling agent by weight.Glass fiber reinforced plastics composite material produced by the present invention has preferable intensity and toughness, pressure resistance, corrosion-resistant, and flame retardant property and good weatherability, can satisfy the high-intensitive of glass toughening manure pit and requires.
Description
Technical field
The present invention relates to glass fibre reinforced plastics technology field more particularly to a kind of fire-retardant resistance to compression composite woods for glass toughening manure pit
Material and preparation method thereof.
Background technique
Glass reinforced plastic, i.e. fiber-reinforced plastic refer generally to unsaturated polyester resin etc. be matrix, with fillers such as glass fibres
Manufactured reinforced plastics, also known as fiberglass reinforced plastics.Have many advantages, such as that light and hard, mechanical strength is preferable, non-conductive,
It has been developed that and is applied to the civil field that septic tank etc. is conducive to ecological protection.
Glass toughening manure pit can effectively solve traditional brick and mix the leakage of septic tank, different degrees of caused by underground water source
The problems such as polluting and inclination caused to building, and base can be established to carry out successive depths processing to the sewage of discharge
Plinth.But the intensity of existing glass toughening manure pit is in practical application popularization that there is also certain drawbacks, and due in septic tank
Containing a large amount of imflammable gas, so also having while ability is weighed in the resistance to compression for reinforcing glass toughening manure pit to its anti-flammability
Certain requirement.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of fire-retardant resistance to compressions for glass toughening manure pit
Composite material and preparation method, glass fiber reinforced plastics composite material obtained have preferable intensity and toughness, pressure resistance, corrosion-resistant, and
Flame retardant property is good.
A kind of fire-retardant resistance to compression composite material for glass toughening manure pit proposed by the present invention, raw material wrap by weight
Include: 100 parts of unsaturated polyester resin, 3-7 parts of acrylonitrile-butadiene-styrene copolymer, 80-110 parts of glass fibre, silicon are micro-
3-7 parts of powder, 20-30 parts of bentonite, 6-12 parts of epoxy propane butyl ether, 3-7 parts of curing agent, 2-5 parts of promotor, fire retardant 2-5
Part, 0.5-2 parts of benzotriazole, 0.5-2 parts of butyl benzyl phthalate, 1-3 parts of coupling agent.
Preferably, the bentonite is modified alta-mud, is prepared as follows: bentonite being distributed in water and prepares suspension
Liquid, is added dodecyl trimethyl ammonium chloride solution, ultrasonic disperse thereto, and heating is stirred to react, is added after reaction dense
Salt acid for adjusting pH, is stirred to react, and filters, dry, obtains material a；Material a is added to the water, ultrasound adds fructose, stirs, so
It is placed in autoclave and carries out hydro-thermal reaction, filter, wash, it is dry, obtain material b；Material b is added by concentrated nitric acid and the concentrated sulfuric acid
In the nitration mixture of composition, heating water bath is stirred to react, and is filtered, washing, it is dry to get.
Preferably, the modified alta-mud prepare it is as follows: 10 parts of bentonites are distributed in water and prepare the outstanding of 6-10%
Supernatant liquid, is added 4-7 parts of 22-27% dodecyl trimethyl ammonium chloride solution thereto, and ultrasonic disperse 40-60min is warming up to
50-60 DEG C, it is stirred to react 8-12h, concentrated hydrochloric acid is added after reaction and adjusts pH to 2-3, is stirred to react 3-5h, filters, it is dry,
Obtain material a；Material a is added in 400-500 parts of water, ultrasonic disperse 20-40min adds 9-14 parts of fructose, stirring and dissolving,
It is subsequently placed in autoclave the hydro-thermal reaction 2.5-3.5h at 170-190 DEG C, is filtered, is washed, it is dry, obtain material b；By material b
It being added in the nitration mixture being made of concentrated nitric acid and the concentrated sulfuric acid, heating water bath is stirred to react 1-2h to 50-60 DEG C, it filters, washing,
It is dry to get.
Preferably, dodecyl trimethyl ammonium chloride solution, ultrasonic disperse is added, heating is stirred to react, speed of agitator is
200-300r/min。
Preferably, concentrated hydrochloric acid is added and adjusts pH, be stirred to react, speed of agitator 700-800r/min.
Preferably, the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1:2-4 in nitration mixture.
Preferably, the partial size D of the silicon powder is 0.01-5 μm.
Preferably, the fire retardant is at least one of ammonium polyphosphate, aluminium hydroxide, deca-BDE.
The invention also provides the preparation methods of the above-mentioned fire-retardant resistance to compression composite material for glass toughening manure pit, and step is such as
Under: by unsaturated polyester resin, acrylonitrile-butadiene-styrene copolymer, glass fibre, silicon powder, bentonite, epoxy third
Alkane butyl ether, promotor, fire retardant, benzotriazole, butyl benzyl phthalate, coupling agent mixing, stirring add solidification
Agent, stirring, be injected into mold solidify to get.
The utility model has the advantages that being with insatiable hunger the invention proposes a kind of fire-retardant resistance to compression composite material for glass toughening manure pit
It is basis material with polyester resin, and adds acrylonitrile-butadiene-styrene copolymer, has glass steel substrate good
Intensity and toughness, and glass fiber reinforcement is added, improve the mechanical properties such as the shock resistance of glass reinforced plastic；Bentonitic addition improves multiple
The mechanical property and flame retardant property of condensation material, with silicon powder cooperate, basis material can it is evenly dispersed and filling, improve product
Compactness, and then improve composite material mechanical property, then with epoxy propane butyl ether, promotor, fire retardant, benzo three
The ingredients such as azoles, butyl benzyl phthalate, coupling agent synergistic effect, glass fiber reinforced plastics composite material obtained have preferable intensity
With toughness, pressure resistance, corrosion-resistant, and flame retardant property and good weatherability can satisfy the high-intensitive of glass toughening manure pit and require.
In the preparation of modified alta-mud, bentonite is carried out using dodecyl trimethyl ammonium chloride by ion-exchange
It is modified, enter between montmorillonite layer and expand its interlamellar spacing, sheet surfaces are covered by long alkyl chain so as to improve its surface hydrophobicity
Property, it adds concentrated hydrochloric acid and carries out acidification, the K between cheating engaging layer+、Na+、Ca2+、Mg2+Etc. cation ic-converted for the solvable of acid
Property salt and dissolve out, to weaken the binding force of original interlayer, so that interlayer lattice is split, further expansion interlamellar spacing, and make
Montmorillonite becomes organophilic from hydrophily, facilitates unsaturated polyester resin and is further inserted into piece interlayer, improves the phase of the two
Capacitive, then place it in and carry out hydro-thermal reaction in fructose soln in autoclave, successfully carbosphere is grafted in montmorillonite,
The carbosphere is subjected to oxidation processes with nitration mixture again, so that reactive functional groups silanol group is introduced on its surface, with original
Expect the action of coupling agents in component, improves it in the dispersibility and compatibility of polymer, and due to the introducing of carbosphere, improve
The intensity and anti-flammability of montmorillonite, are added in unsaturated polyester material, and compatibility is good, and can significantly improve material
The mechanical properties such as intensity and anti-flammability.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of fire-retardant resistance to compression composite material for glass toughening manure pit proposed by the present invention, raw material wrap by weight
Include: 100 parts of unsaturated polyester resin, 3 parts of acrylonitrile-butadiene-styrene copolymer, 80 parts of glass fibre, 3 parts of silicon powder,
20 parts of bentonite, 6 parts of epoxy propane butyl ether, 3 parts of curing agent, 2 parts of promotor, 2 parts of fire retardant, 0.5 part of benzotriazole, adjacent benzene
0.5 part of diformazan acid butyl benzyl ester, 1 part of coupling agent；
Wherein, the partial size D of silicon powder is 0.01-5 μm；Fire retardant is ammonium polyphosphate, and curing agent is methyl ethyl ketone peroxide, is promoted
It is cobalt naphthenate, coupling agent KH550 into agent.
The invention also provides the preparation methods of the above-mentioned fire-retardant resistance to compression composite material for glass toughening manure pit, and step is such as
Under: by unsaturated polyester resin, acrylonitrile-butadiene-styrene copolymer, glass fibre, silicon powder, bentonite, epoxy third
Alkane butyl ether, promotor, fire retardant, benzotriazole, butyl benzyl phthalate, coupling agent mixing, stirring add solidification
Agent, stirring, be injected into mold solidify to get.
Embodiment 2
A kind of fire-retardant resistance to compression composite material for glass toughening manure pit proposed by the present invention, raw material wrap by weight
Include: 100 parts of unsaturated polyester resin, 7 parts of acrylonitrile-butadiene-styrene copolymer, 110 parts of glass fibre, 7 parts of silicon powder,
30 parts of bentonite, 12 parts of epoxy propane butyl ether, 7 parts of curing agent, 5 parts of promotor, 5 parts of fire retardant, 2 parts of benzotriazole, adjacent benzene
2 parts of diformazan acid butyl benzyl ester, 3 parts of coupling agent；
Wherein, the partial size D of silicon powder is 0.01-5 μm；Fire retardant is aluminium hydroxide, and curing agent is methyl ethyl ketone peroxide, is promoted
It is cobalt naphthenate, coupling agent KH550 into agent.
The invention also provides the preparation methods of the above-mentioned fire-retardant resistance to compression composite material for glass toughening manure pit, and step is such as
Under: by unsaturated polyester resin, acrylonitrile-butadiene-styrene copolymer, glass fibre, silicon powder, bentonite, epoxy third
Alkane butyl ether, promotor, fire retardant, benzotriazole, butyl benzyl phthalate, coupling agent mixing, stirring add solidification
Agent, stirring, be injected into mold solidify to get.
Embodiment 3
A kind of fire-retardant resistance to compression composite material for glass toughening manure pit proposed by the present invention, raw material wrap by weight
Include: 100 parts of unsaturated polyester resin, 4 parts of acrylonitrile-butadiene-styrene copolymer, 100 parts of glass fibre, 5 parts of silicon powder,
25 parts of bentonite, 10 parts of epoxy propane butyl ether, 5 parts of curing agent, 4 parts of promotor, 3 parts of fire retardant, 1 part of benzotriazole, adjacent benzene
1 part of diformazan acid butyl benzyl ester, 2 parts of coupling agent；
Wherein, bentonite is modified alta-mud, prepare it is as follows: by 10 parts of bentonites be distributed in water prepare 6% hang
Supernatant liquid, is added 4 parts of 22% dodecyl trimethyl ammonium chloride solution thereto, and ultrasonic disperse 40min is warming up to 50 DEG C, stirs
Reaction 8h, speed of agitator 200r/min are mixed, concentrated hydrochloric acid is added after reaction and adjusts pH to 2, is stirred to react 3h, speed of agitator
For 700r/min, filter, it is dry, obtain material a；Material a is added in 400 parts of water, ultrasonic disperse 20min adds 9 portions of fruits
Sugar, stirring and dissolving are subsequently placed in autoclave the hydro-thermal reaction 2.5h at 170 DEG C, filter, and wash, dry, obtain material b；By object
Material b is added to by the concentrated nitric acid that volume ratio is 1:2 and the nitration mixture that the concentrated sulfuric acid forms, heating water bath is stirred to react 1h to 50 DEG C,
Filter, washing, it is dry to get；
Wherein, the partial size D of silicon powder is 0.01-5 μm；Fire retardant be ammonium polyphosphate, aluminium hydroxide according to 1:1 weight ratio
Composition, curing agent is methyl ethyl ketone peroxide, and promotor is cobalt naphthenate, coupling agent KH550.
The invention also provides the preparation methods of the above-mentioned fire-retardant resistance to compression composite material for glass toughening manure pit, and step is such as
Under: by unsaturated polyester resin, acrylonitrile-butadiene-styrene copolymer, glass fibre, silicon powder, bentonite, epoxy third
Alkane butyl ether, promotor, fire retardant, benzotriazole, butyl benzyl phthalate, coupling agent mixing, stirring add solidification
Agent, stirring, be injected into mold solidify to get.
Embodiment 4
A kind of fire-retardant resistance to compression composite material for glass toughening manure pit proposed by the present invention, raw material wrap by weight
Include: 100 parts of unsaturated polyester resin, 5 parts of acrylonitrile-butadiene-styrene copolymer, 90 parts of glass fibre, 4 parts of silicon powder,
28 parts of bentonite, 8 parts of epoxy propane butyl ether, 4.5 parts of curing agent, 3.5 parts of promotor, 2.5 parts of fire retardant, benzotriazole 1.5
Part, 1.5 parts of butyl benzyl phthalate, 1.5 parts of coupling agent；
Wherein, bentonite is modified alta-mud, prepare it is as follows: by 10 parts of bentonites be distributed in water prepare 10% hang
Supernatant liquid, is added 7 parts of 27% dodecyl trimethyl ammonium chloride solution thereto, and ultrasonic disperse 60min is warming up to 60 DEG C, stirs
Reaction 12h, speed of agitator 300r/min are mixed, concentrated hydrochloric acid is added after reaction and adjusts pH to 3, is stirred to react 5h, stirring turns
Speed is 800r/min, is filtered, dry, obtains material a；Material a is added in 500 parts of water, ultrasonic disperse 40min adds 14 parts
Fructose, stirring and dissolving are subsequently placed in autoclave the hydro-thermal reaction 3.5h at 190 DEG C, filter, and wash, dry, obtain material b；It will
Material b is added to by the concentrated nitric acid that volume ratio is 1:4 and the nitration mixture that the concentrated sulfuric acid forms, heating water bath is stirred to react to 60 DEG C
2h is filtered, washing, it is dry to get；
Wherein, the partial size D of silicon powder is 0.01-5 μm；Fire retardant is the weight of ammonium polyphosphate and deca-BDE according to 1:1
Amount is than composition, and curing agent is methyl ethyl ketone peroxide, and promotor is cobalt naphthenate, coupling agent KH550.
The invention also provides the preparation methods of the above-mentioned fire-retardant resistance to compression composite material for glass toughening manure pit, and step is such as
Under: by unsaturated polyester resin, acrylonitrile-butadiene-styrene copolymer, glass fibre, silicon powder, bentonite, epoxy third
Alkane butyl ether, promotor, fire retardant, benzotriazole, butyl benzyl phthalate, coupling agent mixing, stirring add solidification
Agent, stirring, be injected into mold solidify to get.
Embodiment 5
A kind of fire-retardant resistance to compression composite material for glass toughening manure pit proposed by the present invention, raw material wrap by weight
Include: 100 parts of unsaturated polyester resin, 6 parts of acrylonitrile-butadiene-styrene copolymer, 95 parts of glass fibre, 6 parts of silicon powder,
26 parts of bentonite, 10 parts of epoxy propane butyl ether, 6 parts of curing agent, 4.5 parts of promotor, 3.5 parts of fire retardant, benzotriazole 1.2
Part, 0.8 part of butyl benzyl phthalate, 2.5 parts of coupling agent；
Wherein, bentonite is modified alta-mud, prepare it is as follows: by 10 parts of bentonites be distributed in water prepare 8% hang
Supernatant liquid, is added 6 parts of 25% dodecyl trimethyl ammonium chloride solution thereto, and ultrasonic disperse 50min is warming up to 55 DEG C, stirs
Reaction 10h, speed of agitator 250r/min are mixed, concentrated hydrochloric acid is added after reaction and adjusts pH to 2.5, is stirred to react 4h, stirs
Revolving speed is 750r/min, is filtered, dry, obtains material a；Material a is added in 450 parts of water, ultrasonic disperse 30min adds 12
Part fructose, stirring and dissolving are subsequently placed in autoclave the hydro-thermal reaction 3h at 180 DEG C, filter, and wash, dry, obtain material b；It will
Material b is added to by the concentrated nitric acid that volume ratio is 1:3 and the nitration mixture that the concentrated sulfuric acid forms, heating water bath is stirred to react to 55 DEG C
1.5h is filtered, washing, it is dry to get；
Wherein, the partial size D of silicon powder is 0.01-5 μm；Fire retardant is the weight of ammonium polyphosphate and aluminium hydroxide according to 1:1
Than composition, curing agent is methyl ethyl ketone peroxide, and promotor is cobalt naphthenate, coupling agent KH550.
The invention also provides the preparation methods of the above-mentioned fire-retardant resistance to compression composite material for glass toughening manure pit, and step is such as
Under: by unsaturated polyester resin, acrylonitrile-butadiene-styrene copolymer, glass fibre, silicon powder, bentonite, epoxy third
Alkane butyl ether, promotor, fire retardant, benzotriazole, butyl benzyl phthalate, coupling agent mixing, stirring add solidification
Agent, stirring, be injected into mold solidify to get.
Embodiment 6
Compared with Example 5, the bentonite that difference is only that in fire-retardant resistance to compression composite material is unmodified bentonite.
The performance of the fire-retardant resistance to compression composite material of glass toughening manure pit obtained in 1-6 of the embodiment of the present invention is examined
It surveys, test result see the table below.
The performance detection data of 1 glass toughening manure pit composite material of table
From table 1 it follows that the glass toughening manure pit composite material in the application has preferable impact strength and resists
Compressive Strength, and compared to unmodified bentonitic composite material is contained, using the composite material of the composite material of modified alta-mud
Mechanical property, anti-flammability all increases.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of fire-retardant resistance to compression composite material for glass toughening manure pit, which is characterized in that its raw material includes: not by weight
100 parts of saturated polyester resin, 3-7 parts of acrylonitrile-butadiene-styrene copolymer, 80-110 parts of glass fibre, silicon powder 3-7
Part, 20-30 parts of bentonite, 6-12 parts of epoxy propane butyl ether, 3-7 parts of curing agent, 2-5 parts of promotor, 2-5 parts of fire retardant, benzene
And 0.5-2 parts of triazole, 0.5-2 parts of butyl benzyl phthalate, 1-3 parts of coupling agent.
2. the fire-retardant resistance to compression composite material according to claim 1 for glass toughening manure pit, which is characterized in that described swollen
Profit soil is modified alta-mud, prepares as follows: bentonite is distributed to formulated suspension in water, and dodecyl three is added thereto
Methyl chloride ammonium salt solution, ultrasonic disperse, heating are stirred to react, and concentrated hydrochloric acid is added after reaction and adjusts pH, is stirred to react, takes out
Filter, it is dry, obtain material a；Material a is added to the water, ultrasound adds fructose, stirs, is subsequently placed in autoclave and carries out hydro-thermal
Reaction filters, and washs, dry, obtains material b；Material b is added in the nitration mixture being made of concentrated nitric acid and the concentrated sulfuric acid, heating water bath,
Be stirred to react, filter, washing, it is dry to get.
3. the fire-retardant resistance to compression composite material according to claim 1 or 2 for glass toughening manure pit, which is characterized in that institute
It is as follows to state preparing for modified alta-mud: 10 parts of bentonites being distributed to the suspension for preparing 6-10% in water, 4-7 is added thereto
The 22-27% dodecyl trimethyl ammonium chloride solution of part, ultrasonic disperse 40-60min are warming up to 50-60 DEG C, are stirred to react 8-
Concentrated hydrochloric acid is added after reaction and adjusts pH to 2-3, is stirred to react 3-5h, filters by 12h, dry, obtains material a；Material a is added
Enter in 400-500 parts of water, ultrasonic disperse 20-40min, add 9-14 parts of fructose, stirring and dissolving is subsequently placed in autoclave
Hydro-thermal reaction 2.5-3.5h at 170-190 DEG C is filtered, and is washed, dry, obtains material b；Material b is added to by concentrated nitric acid and dense
In the nitration mixture of sulfuric acid composition, heating water bath is stirred to react 1-2h to 50-60 DEG C, filters, washing, it is dry to get.
4. the fire-retardant resistance to compression composite material according to claim 2 or 3 for glass toughening manure pit, which is characterized in that add
Enter dodecyl trimethyl ammonium chloride solution, ultrasonic disperse, heating is stirred to react, speed of agitator 200-300r/min.
5. according to the described in any item fire-retardant resistance to compression composite materials for glass toughening manure pit of claim 2-4, feature exists
In addition concentrated hydrochloric acid adjusts pH, is stirred to react, speed of agitator 700-800r/min.
6. according to the described in any item fire-retardant resistance to compression composite materials for glass toughening manure pit of claim 2-5, feature exists
In the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 1:2-4 in nitration mixture.
7. the fire-retardant resistance to compression composite material according to claim 1-6 for glass toughening manure pit, feature exist
In the partial size D of the silicon powder is 0.01-5 μm.
8. -7 any fire-retardant resistance to compression composite material for glass toughening manure pit according to claim 1, which is characterized in that
The fire retardant is at least one of ammonium polyphosphate, aluminium hydroxide, deca-BDE.
9. a kind of preparation based on the described in any item fire-retardant resistance to compression composite materials for glass toughening manure pit of claim 1-8
Method, which is characterized in that steps are as follows: by unsaturated polyester resin, acrylonitrile-butadiene-styrene copolymer, glass fibers
Dimension, silicon powder, bentonite, epoxy propane butyl ether, promotor, fire retardant, benzotriazole, butyl benzyl phthalate, idol
Join agent mixing, stirring, add curing agent, stir, be injected into mold solidify to get.
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| CN112794954A (en) * | 2019-11-14 | 2021-05-14 | 邵阳千两新型环保建材有限公司 | Heat-resistant glass fiber reinforced plastic material |
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