CN106590193A - Antiseptic polystyrene building material loading transition metal and preparing method thereof - Google Patents
Antiseptic polystyrene building material loading transition metal and preparing method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/06—Polystyrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses an antiseptic polystyrene building material loading transition metal. The antiseptic polystyrene building material is prepared from, by weight, 6-8 parts of zirconium oxychloride, 7-9 parts of nickel chloride, 10-14 parts of graphene oxide, 20-30 parts of styrene, 0.1-0.2 part of dibenzoyl peroxide, 100-110 parts of polystyrene, 0.3-1 part of salicylanilide, 2-3 parts of ammonium metaborate, 1-2 parts of triphenyl(phenylmethyl)-phosphonium chloride, 0.7-1 part of sodium benzoate, 0.8-2 part of diazolidinyl urea, 1-2 parts of octyl isothiazolinone, 6-7 parts of wollastonite powder and 1-3 parts of oxidized polyethlene wax. As octyl isothiazolinone, triphenyl(phenylmethyl)-phosphonium chloride and sodium benzoate are added, the antiseptic performance and comprehensive performance of the finished product can be effectively improved.
Description
Technical field
The present invention relates to building material technical field, more particularly to a kind of polystyrene building of anti-corrosion carrying transition metal
Material and preparation method thereof.
Background technology
Polymer nanocomposites(By polymeric matrix(Continuous phase)With nano-filled dose(Dispersion phase)Composition.Wherein,
The yardstick of nano-filled dose of at least one dimension is less than nanometer.Good dividing is formed in polymeric matrix when nano-filled dose
Dissipate, can significantly improve the performance of nano composite material.Compared to traditional polymer composites, polymer nanocomposite composite wood
The consumption of the filler of material is low, effect is significant;
The performance of polymer nanocomposites is affected by two big factors:Nano-filled dose of dispersibility and nano-filled dose with
Interfacial interaction between polymeric matrix;Dispersibility(Dispersibility refers to dispersion feelings of the nanoparticle in polymeric matrix
Condition.Nanoparticle generally has stronger reunion tendency, and the specific surface area for causing filler reduces, affects between filler and matrix
Surface energy and interfacial interaction, so as to affect the performance of composite, interfacial interaction:Nano-filled dose and polymer
Interfacial interaction between matrix is the key factor for causing changes in material properties, and important to being dispersed with for nanoparticle
Affect.When interfacial interaction is stronger, nanoparticle easily forms good dispersion, and the performance of composite is improved more
Substantially;
Polymer laminar compound nano composite has lot of advantages, and first, dispersion phase is two-dimensional layer nano material, than
Surface area is big;Secondly, two-dimensional layered structure forms lamella blocking effect, can significantly increase material gas barrier property and
Heat stability;Again, many performances can simultaneously be improved;
The fire safety performance of polymeric material is the important topic that polymer grinds the field of making internal disorder or usurp.The fire of polymer
Safety refers to security performance during polymer combustion, mainly discharges, poisons including ignition temperature, the combustion heat
The contents such as the release of property flue gas.Polymer is widely used in the every field of human being's production and life.Most polymers
Main component be carbon and hydrogen, be susceptible to decompose and burn when being heated, belong to combustible material.During polymer combustion, release
Substantial amounts of light, heat and toxic flue gas are released, is the main cause for causing casualties in fire.Improve polymeric material fire peace
The technology of full performance is commonly known as flame-retarded technology;
Improving the method for flame retardance of polymer performance can be divided into two big class, and the first kind is, by MOLECULE DESIGN, to give polymer point
Sub- ignition-proof element or flame retarding construction, so as to improve the fire resistance of polymer;Equations of The Second Kind is by adding fire retardant, so as to improve
The fire resistance of polymeric material.Wherein, Equations of The Second Kind is the wide variety of method of plastics industry, with technology maturation, low cost
And it is easy to process the advantages of.Conventional fire retardant has bromide fire retardant, APP, hydroxide trick, magnesium hydroxide, red phosphorus and three
Poly cyanamid etc..Over nearly 15 years, flame-retardant polymer nano composite material has obtained extensive research.Wherein, polymer laminar without
Machine thing nano composite material, it is only necessary to less addition, you can obtain obvious flame retardant effect, and environmental protection, be considered
One of important developing direction of field of fire-proof technology;
The lamella blocking effect of graphene sheet layer is the heat stability and fire safety for improving graphene/polymer nano composite material
The principal element of performance, and its high-termal conductivity often leads to the reduction of polymer nanocomposites pyrolysis temperature, ignition temperature and carries
Before.But, with regard to the interfacial interaction between Graphene and polymer in GPNC heat stability and fire safety performance is improved
Effect, also clearly do not studied;The high-termal conductivity of Graphene is unfavorable for that it improves polymer thermostable and fire peace
Full performance.The physics and chemical property of Graphene can be changed by surface modification, so as to open up a raising Graphene/polymerization
The technology path of thing nano composite material heat stability and fire safety performance.The research of flame retardance of polymer technical field shows, portion
Divide transition metal that there is the effect of catalyzing and carbonizing and capture free radical, be conducive to improving the heat stability and anti-flammability of polymer
Can, such as, zirconium is acted in the pyrolysis of polymer and combustion process with catalysis carbon-forming, and nickel is not only acted on catalysis carbon-forming,
Also there is the effect of absorption free radical.Therefore, transition metal is supported on Graphene, it is possible to have than simple Graphene
Preferably improve the effect of heat stability and fire safety performance.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of polyphenyl second of anti-corrosion carrying transition metal
Alkene construction material and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of polystyrene construction material of anti-corrosion carrying transition metal, it is by made by the raw material of following weight parts:
Zirconium oxychloride 6-8, Nickel dichloride. 7-9, graphene oxide 10-14, styrene 20-30, dibenzoyl peroxide 0.1-0.2,
Polystyrene 100-110, n- N-phenylsalicylamide 0.3-1, ammonium metaborate 2-3, benzyl triphenyl phosphonium chloride phosphine 1-2, sodium benzoate
0.7-1, double imidazolidinyl urea 0.8-2, octylisothiazolinone 1-2, wollastonite in powder 6-7, OPE 1-3.
A kind of preparation method of the polystyrene construction material of described anti-corrosion carrying transition metal, comprises the following steps:
(1)Above-mentioned wollastonite in powder is calcined into 1-2 hours at 700-800 DEG C, is cooled down, be added to the sodium hydroxide of 3-5mol/l
In, it is 51-60 DEG C to rise high-temperature, insulated and stirred 20-30 minute, adds ammonium metaborate, is stirred, and Deca concentration is 90-95%
Sulphuric acid, regulation pH be 1-2, stirring reaction 30-40 minute, filter, will precipitation washing 3-4 time, normal temperature drying obtains modified stone
Powder;
(2)By above-mentioned graphene oxide, modified stone powder mixing, in being added to the deionized water of compound weight 200-300 times, surpass
Sonication 100-120 minutes, obtain graphene dispersing solution;
(3)Above-mentioned double imidazolidinyl urea is added in the dehydrated alcohol of its weight 6-10 times, is stirred, rising high-temperature is
51-70 DEG C, insulated and stirred 3-5 minute, add OPE, in being sent to 110-120 DEG C of oil bath, insulated and stirred 10-
20 minutes, discharging added octylisothiazolinone, stirs to room temperature, obtains alcohol dispersion liquid;
(4)Above-mentioned zirconium oxychloride, Nickel dichloride. are mixed, in being added to the deionized water of compound weight 70-100 times, stirring is equal
It is even, mix with above-mentioned graphene dispersing solution, stir, in being sent to reactor, Deca concentration is the ammonia of 10-14%, adjusts
PH is 10-11, and it is 190-200 DEG C to rise high-temperature, insulated and stirred 6-7 hour, discharging, sucking filtration, by precipitation washing 2-3 time, in 76-
20-25 hours are dried at 80 DEG C, pretreating graphite alkene is obtained;
(5)Above-mentioned pretreating graphite alkene is added in the dimethylformamide of its weight 100-110 times, ultrasonic 1-2 hours are obtained
Amide dispersion liquid;
(6)Above-mentioned styrene is added in the dimethylformamide of its weight 17-20 times, 16-20 minutes is stirred, with above-mentioned acyl
Amine dispersion liquid mixes, and stirs, and adds dibenzoyl peroxide, is passed through nitrogen, the insulated and stirred 1-2 hour at 70-75 DEG C,
In sending into baking oven, complete, discharging cooling is dried at 120-130 DEG C, obtains polymer modification Graphene;
(7)Above-mentioned polymer modification Graphene is added in alcohol dispersion liquid, it is 41-60 DEG C to rise high-temperature, adds above-mentioned n- water
Poplar anilide, insulated and stirred 10-15 minute, obtains graphene dispersing solution;
(8)Above-mentioned graphene dispersing solution, polystyrene are mixed, is stirred, add remaining each raw material, be sent to banbury
In, it is 180-190 DEG C to rise high-temperature, Heat preservation 10-12 minutes, room temperature is cooled to, in sending into vulcanizing press, in 190-
200 DEG C, under 10-15MPa, fine powder is worn in pressurize 3-4 minutes, cooling, obtains final product.
It is an advantage of the invention that:Zirconium oxide and hydroxide that the present invention passes through the monoclinic phase in graphite oxide area load
Nickel, and while graphite oxide is reduced to into Graphene, the heat stability of composite depends on the lamella obstruct of graphene sheet layer
Interfacial interaction between effect and Graphene and polymer, and the basic structure of Graphene is conjugation hexatomic ring, it is and poly-
There is π-π interactions in the phenyl ring in styrene, form good leafing dispersity, effectively raises Graphene and is polymerized
Interfacial interaction between thing, the heat that carrying transition metal can further improve graphite dilute polymer nano composite material is steady
, there is synergistic effect in qualitative and fire safety performance, there is 2 reasons between the zirconium or nickel and graphite coal of the present invention:Zirconium is in polymer
Pyrolysis and combustion process in catalysis carbon-forming effect, can promote material formed protectiveness layer of charcoal, nickel not only have urge
Chemical conversion charcoal effect, also with the effect of absorption free radical;And graphite is dilute with more preferable lamella blocking effect, so as to reduce pyrolysis
The diffusion of product and effusion;Effectively raise the heat stability and fire resistance of finished product;The octyl group isothiazole that the present invention is added
Quinoline ketone, benzyl triphenyl phosphonium chloride phosphine, sodium benzoate etc., can effectively improve the antiseptic property of finished-product material, improve finished product
Combination property.
Specific embodiment
A kind of polystyrene construction material of anti-corrosion carrying transition metal, it is by made by the raw material of following weight parts:
Zirconium oxychloride 6, Nickel dichloride. 7, graphene oxide 10, styrene 20, dibenzoyl peroxide 0.1, polystyrene 100, n water
Poplar anilide 0.3, ammonium metaborate 2, benzyl triphenyl phosphonium chloride phosphine 1, sodium benzoate 0.7, the different thiophene of double imidazolidinyl urea 0.8, octyl group
Oxazoline ketone 1, wollastonite in powder 6, OPE 1.
A kind of preparation method of the polystyrene construction material of described anti-corrosion carrying transition metal, comprises the following steps:
(1)Above-mentioned wollastonite in powder is calcined 1 hour at 700 DEG C, is cooled down, in being added to the sodium hydroxide of 3mol/l, rise high temperature
Spend for 51 DEG C, insulated and stirred 20 minutes adds ammonium metaborate, stirs, and Deca concentration is 90% sulphuric acid, it is 1 to adjust pH,
Stirring reaction 30 minutes, filters, and by precipitation washing 3 times, normal temperature drying obtains modified stone powder;
(2)By above-mentioned graphene oxide, modified stone powder mixing, in being added to the deionized water of 200 times of compound weight, at ultrasound
Reason 100 minutes, obtains graphene dispersing solution;
(3)Above-mentioned double imidazolidinyl urea is added in the dehydrated alcohol of 6 times of its weight, is stirred, it is 51 DEG C to rise high-temperature,
Insulated and stirred 3 minutes, adds OPE, and in being sent to 110 DEG C of oil bath, insulated and stirred 10 minutes, discharging is added pungent
Base isothiazolone, stirs to room temperature, obtains alcohol dispersion liquid;
(4)Above-mentioned zirconium oxychloride, Nickel dichloride. are mixed, in being added to the deionized water of 70 times of compound weight, is stirred, with
Above-mentioned graphene dispersing solution mixing, stirs, and in being sent to reactor, Deca concentration is 10% ammonia, and it is 10 to adjust pH,
It is 190 DEG C to rise high-temperature, insulated and stirred 6 hours, discharging, and sucking filtration, by precipitation washing 2 times, is dried 20 hours at 76 DEG C, obtains pre-
Process Graphene;
(5)Above-mentioned pretreating graphite alkene is added in the dimethylformamide of 100 times of its weight, ultrasound 1 hour obtains amide point
Dispersion liquid;
(6)Above-mentioned styrene is added in the dimethylformamide of 17 times of its weight, is stirred 16 minutes, with the dispersion of above-mentioned amide
Liquid mixes, and stirs, and adds dibenzoyl peroxide, is passed through nitrogen, insulated and stirred 1 hour at 70 DEG C, in sending into baking oven,
Complete, discharging cooling is dried at 120 DEG C, polymer modification Graphene is obtained;
(7)Above-mentioned polymer modification Graphene is added in alcohol dispersion liquid, it is 41 DEG C to rise high-temperature, adds above-mentioned n salicyloyls
Aniline, insulated and stirred 10 minutes, obtains graphene dispersing solution;
(8)Above-mentioned graphene dispersing solution, polystyrene are mixed, is stirred, add remaining each raw material, be sent to banbury
In, it is 180 DEG C to rise high-temperature, and Heat preservation 10 minutes is cooled to room temperature, in sending into vulcanizing press, in 190 DEG C, 10MPa
Under, fine powder is worn in pressurize 3 minutes, cooling, obtains final product.
Performance test:
Tensile strength(MPa):12.4;
Elongation at break(%):76;
Bending strength(MPa):23.7.
Claims (2)
1. a kind of polystyrene construction material of anti-corrosion carrying transition metal, it is characterised in that it is by the original of following weight parts
Made by material:
Zirconium oxychloride 6-8, Nickel dichloride. 7-9, graphene oxide 10-14, styrene 20-30, dibenzoyl peroxide 0.1-0.2,
Polystyrene 100-110, n- N-phenylsalicylamide 0.3-1, ammonium metaborate 2-3, benzyl triphenyl phosphonium chloride phosphine 1-2, sodium benzoate
0.7-1, double imidazolidinyl urea 0.8-2, octylisothiazolinone 1-2, wollastonite in powder 6-7, OPE 1-3.
2. a kind of preparation method of the polystyrene construction material of anti-corrosion carrying transition metal as claimed in claim 1, it is special
Levy and be, comprise the following steps:
(1)Above-mentioned wollastonite in powder is calcined into 1-2 hours at 700-800 DEG C, is cooled down, be added to the sodium hydroxide of 3-5mol/l
In, it is 51-60 DEG C to rise high-temperature, insulated and stirred 20-30 minute, adds ammonium metaborate, is stirred, and Deca concentration is 90-95%
Sulphuric acid, regulation pH be 1-2, stirring reaction 30-40 minute, filter, will precipitation washing 3-4 time, normal temperature drying obtains modified stone
Powder;
(2)By above-mentioned graphene oxide, modified stone powder mixing, in being added to the deionized water of compound weight 200-300 times, surpass
Sonication 100-120 minutes, obtain graphene dispersing solution;
(3)Above-mentioned double imidazolidinyl urea is added in the dehydrated alcohol of its weight 6-10 times, is stirred, rising high-temperature is
51-70 DEG C, insulated and stirred 3-5 minute, add OPE, in being sent to 110-120 DEG C of oil bath, insulated and stirred 10-
20 minutes, discharging added octylisothiazolinone, stirs to room temperature, obtains alcohol dispersion liquid;
(4)Above-mentioned zirconium oxychloride, Nickel dichloride. are mixed, in being added to the deionized water of compound weight 70-100 times, stirring is equal
It is even, mix with above-mentioned graphene dispersing solution, stir, in being sent to reactor, Deca concentration is the ammonia of 10-14%, adjusts
PH is 10-11, and it is 190-200 DEG C to rise high-temperature, insulated and stirred 6-7 hour, discharging, sucking filtration, by precipitation washing 2-3 time, in 76-
20-25 hours are dried at 80 DEG C, pretreating graphite alkene is obtained;
(5)Above-mentioned pretreating graphite alkene is added in the dimethylformamide of its weight 100-110 times, ultrasonic 1-2 hours are obtained
Amide dispersion liquid;
(6)Above-mentioned styrene is added in the dimethylformamide of its weight 17-20 times, 16-20 minutes is stirred, with above-mentioned acyl
Amine dispersion liquid mixes, and stirs, and adds dibenzoyl peroxide, is passed through nitrogen, the insulated and stirred 1-2 hour at 70-75 DEG C,
In sending into baking oven, complete, discharging cooling is dried at 120-130 DEG C, obtains polymer modification Graphene;
(7)Above-mentioned polymer modification Graphene is added in alcohol dispersion liquid, it is 41-60 DEG C to rise high-temperature, adds above-mentioned n- water
Poplar anilide, insulated and stirred 10-15 minute, obtains graphene dispersing solution;
(8)Above-mentioned graphene dispersing solution, polystyrene are mixed, is stirred, add remaining each raw material, be sent to banbury
In, it is 180-190 DEG C to rise high-temperature, Heat preservation 10-12 minutes, room temperature is cooled to, in sending into vulcanizing press, in 190-
200 DEG C, under 10-15MPa, fine powder is worn in pressurize 3-4 minutes, cooling, obtains final product.
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