CN105907033B - A kind of preparation method of the fire retardant man-made stone comprising nano-perovskite oxide - Google Patents
A kind of preparation method of the fire retardant man-made stone comprising nano-perovskite oxide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/12—Condensation polymers of aldehydes or ketones
- C04B26/122—Phenol-formaldehyde condensation polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/36—Inorganic materials not provided for in groups C04B14/022 and C04B14/04 - C04B14/34
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/63—Flame-proofing agents
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/54—Substitutes for natural stone, artistic materials or the like
- C04B2111/542—Artificial natural stone
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
Abstract
The present invention relates to a kind of preparation methods of the fire retardant man-made stone comprising nano-perovskite oxide, nano-perovskite oxide is jointly added to metal organic framework UIO materials in ternary polyene ester material (talcum konilite/phenolic resin), improve the heat resistance and intensity of artificial stone, reduce the ageing time of artificial stone, it can keep non-degradable for a long time under high temperature action, and preferable flame retardant effect can also be kept, greatly improve LOI loss on ignition indexes.
Description
Technical field
The present invention relates to a kind of preparation methods of the fire retardant man-made stone comprising nano-perovskite oxide, belong to construction material
Field.
Background technology
With the promotion of people's living standard, the improvement of living conditions, interior decoration industry is grown rapidly, decoration material
Dosage is very big, wherein stone material be it is a kind of most generally use, one of most basic building materials are widely used in ground, metope and table top
Mat formation.Lithotome cost of winning is high, pollution is big, and contains a large amount of naturally occurring radioactive substances, to human health damage compared with
Greatly.With the continuous development of Material Field, the performance of artificial stone material is gradually improved, close to be even more than lithotome,
Increasingly received by market and user, is widely used in cabinet, bathroom, ground, wall decoration.But current artificial stone
Material still has that intensity is low, abrasion-resistant surface is poor, flame-proof heat-resistant performance is not strong, the disadvantage of surface gloss difference.
Invention content
For many deficiencies existing for existing artificial stone, the present invention provides a kind of resistances including nano-perovskite oxide
The preparation method of artificial stone is fired, specific preparation process includes：
（1）Prepare LaxSr1-xCoO3With UIO-66,
（2）By 70-90 parts of talcum powder, 50-60 parts of phenolic resin, 6-10 parts of boron trifluoride, 10-20 parts of white carbon, pearl
25-30 parts of rock powder end, 5-15 parts of melamine, 5-15 parts of triethyl phosphate, 5-15 parts of hydroxyapatite, 5-15 parts of mica sheet,
The quartzy 50-70 parts La obtained with above-mentioned stepsxSr1-xCoO35-10 parts of 10-20 parts, UIO-66 mixing, pour into high-speed stirred
Machine is first used 1000 revs/min of speed to stir 30 minutes, is then stirred with 3000 revs/min of speed at 50 DEG C at room temperature
The batch mixing stirred evenly is discharged, is uniformly taped against on making sheet mold by 30min, and then making sheet mold is placed in vacuum environment and is done
Dry curing molding, the artificial stone blank being removed from the molds after solidification carries out fixed thick, polishing to blank, polishing treatment is hindered
Fire artificial stone；Wherein nano-perovskite oxide LaxSr1-xCoO3In, 0.6<x<1.
Wherein, step（1）Middle nano-perovskite LaxSr1-xCoO3Preparation method be：
（a）Lanthanum nitrate, cobalt nitrate, strontium nitrate and nitric acid are weighed in proportion, is dissolved in deionized water, and mixed nitrate is configured to
Salting liquid, wherein nitric acid：Metal ion：The molar ratio of water is（1-4）：（2~4）：70；Separately weighing citric acid is dissolved in deionized water
In, it is configured to citric acid solution, the molar ratio of wherein citric acid and water is（4~8）：40；
（b）Nitrate solution is heated to 70 ~ 80 DEG C, stirs lower dropwise addition citric acid solution, citric acid amount and the gold of addition
The molar ratio for belonging to ion is 1:1~1:2；Nitrate solution and citric acid solution be sufficiently mixed uniformly after with concentrated ammonia liquor tune pH value of solution
To 7；Gel is obtained after being kept for 2 ~ 3 hours at 75 ~ 80 DEG C；
（c）Gained gel is dried into xerogel at 90 ~ 100 DEG C, then handles 0.5 ~ 1 hour, obtains at 350 ~ 400 DEG C
To nano-perovskite oxide La1-XSrXCoO3。
Wherein, step（1）The preparation method of middle UIO-66 is：0.932g ZrC1 are weighed respectively4With 1.32 g terephthaldehydes
Acid is added 24 mL DMF solvents and is dissolved in polytetrafluoroethylliner liner, and 0.665 mL concentrated hydrochloric acids are then added, and mixing is equal
It is even, 5 min are ultrasonically treated, liner is sealed, is put into baking oven in 120 DEG C of heating reaction 16h, then reduces the temperature to room temperature,
By being centrifuged to mixture after reaction, white precipitate, as UiO-66 are obtained in centrifugation bottom of the tube.
Further, step（2）Middle dry solidification forming temperature is 50-65 DEG C, preferably 55-60 DEG C.
Further, the nano-perovskite oxide LaxSr1-xCoO3Average grain diameter be 20-85nm, preferably 20-60nm
Beneficial effects of the present invention：
Phosphorus and phosphorus-containing compound fire retardant are listed as three big flame-retardant systems with halogen system, inorganic system.Triethyl phosphate, hydroxyl phosphorus
The flame retardant effect of the phosphorus series compounds such as lime stone is preferable, because the metaphosphoric acid generated when burning can be grouped to stable poly state, at
For the protective layer of burning point, the contact by combustion things with oxygen can be completely cut off.The phosphoric acid and poly-metaphosphoric acid of generation are all then strong acid, are had
Very strong dehydration property can make polymer dehydration carbonization, and form charring layer in polymer surfaces, reach starvation and prevent combustion
The purpose of burning.
Melamine has the advantages that Halogen, low toxicity, low cigarette, and nitrogenous flame ratardant is preferable in the flame retardant effect of polyester plastics,
It is especially combined with phosphorus flame retardant, Intumscent Flame Retardant System can be formed, by the synergistic effect of the two, can be greatly improved
The flame retardant effect of polyalkenylesters hydrocarbon artificial stone.The application uses melamine and is applied in combination with triethyl phosphate, hydroxyapatite,
And the ratio of three is adjusted, so that three is played synergistic effect, forms Intumscent Flame Retardant System, experiments have shown that, three（Melamine
Amine：Triethyl phosphate：Hydroxyapatite）Best mass ratio is 1:1:1, flame retardant effect can be greatly improved.Nano inorganic oxygen
Compound is the good selection of fire retardant, such as nano magnesia, and nano zine oxide etc. all can serve as nano inorganic oxide resistance
Combustion agent is added in polyene ester material.Due to nano effect, Preparing Organic-inorganic Nano Hybrid Material have more conventional polymer/
Filler compound is incomparable a little, for example density is small, high mechanical strength, inspiratory and permeability, especially heat-resisting
Property and anti-flammability can be greatly improved.Further, some scholars study the clays class laminar silicic acids such as concave convex rod, montmorillonite
The flame retardant property of salt nanocomposite, above-mentioned inorganic material have different degrees of flame retardant effect.Perovskite structure oxide
ABO3 has unique optics, electricity and magnetic performance, is widely used in terms of biological agent ceramics, has thermal stability
It is good, at low cost, absorption oxygen can be carried out according to B selections, A, B atom, which can be mentioned, adjusts Lattice Oxygen quantity and activity.Mesh
It is preceding that resistance is used as using the more excellent nano-perovskite material of structure or similar polymetallic metal composite oxide not yet
Combustible material.
The aerial burning of high-molecular compound is a kind of very fierce oxidation reaction, belongs to chain reaction course.
It is proliferated a large amount of active hydroxyl free radicals in combustion process, when hydroxyl free radical and high-molecular compound meet, generates hydrocarbon
Compound free radical and water, in the presence of oxygen, hydrocarbon radical decomposition, and form new hydroxyl free radical.So
Cycle, makes combustion reaction constantly continue.The mechanism of action of fire retardant is more complicated, including many factors, but mainly by adopting
Burn cycle is prevented with either physically or chemically.
Someone uses fire retardant of the inorganic material zeolite as artificial stone, but zeolite is rigid structure, and bridging oxygen key is opposite
It is shorter, and lack flexibility, there are certain defects.A kind of MOF with ultrastability, is labeled as UiO-66, and chemical formula is
Zr6O4(OH)4(CO2)12, its structure collapse temperature is higher than 500 DEG C.The inorganic gold of high degree of symmetry is carried out in its stability source
Belong to unit Zr6O4(OH)4And the Zr6The strong interaction of octahedra core and carboxyl oxygen O in ligand.One Zr6It is octahedra
Core and 12 terephthalic acid (TPA) ligands form tetrahedron and octahedra two kinds of hole cage, each octahedron cage
On eight faces, it is connected with a tetrahedron cage, this connection type constantly extends in three dimensions, has 6 holes to be formed
The MOFs of diameter.In addition, chemical stability experiments have shown that, UiO-66 have good water-resistance, acid-resisting.
Therefore, the application is soundd out using UIO-66 materials as the material of composite flame-retardant agent, can improve the resistance to height of artificial stone
Warm nature energy, to improve service life.Since metal-organic framework materials are the coordination polymers using metal ion as tie point,
It, both can be using imidazole skeleton in polymer and phenolic resin material on high molecular chemical characters when being combined with phenolic resin material
Compatibility, form resulting structure, using tetrahedral structure can effective dispersion space charge, avoid the aggregation of space charge,
Improve high temperature resistant, ageing-resistant performance；On the other hand, contain metal ion in UIO, inorganic compound can be formed, and it is inorganization
It is one of fire retardant of this field to close object such as nano inorganic magnesia, iron oxide etc., can be with after being combined with phenolic resin material
Using the complementation of inorganic material, further strengthen the charge transport efficiency of artificial stone, improves flame retardant property, improve artificial
High temperature resistant, the ageing-resistant performance of stone.
The present invention uses nano-perovskite oxide La for the first timexSr1-xCoO3（0.6<x<1）As inorganic nano fire retardant at
Point, it is added in polyene ester material, due to the addition of nano-perovskite, thus it is possible to vary transfer ways of the carrier in medium,
Trap level is reduced, carrier is made to be easy to, along transporting perpendicular to thickness direction, effectively inhibit the note of carrier through-thickness
Enter weakens extra electric field to a certain extent with accumulation semi-conductive layers of the space charge in medium on thickness of sample direction,
Semi-conductive layer and the field strength at interfacial dielectric layer are reduced, reduces the space charge amount of cathode injection, after short circuit in sample most
Remaining a small amount of space charge eventually, reduces the aggregation of charge, improves the electricity saving performance of material, improve the anti-ageing of artificial stone
Change, high temperature resistance, plays efficient fire-retardant purpose.
The application main material is ternary material：Talcum powder, quartz, phenolic resin mixing, composite high-molecular type are expanded, are had
Conducive to the complementary structure of various high molecular materials, being in direct contact for composite flame-proof agent material and polyalkenylesters is combined closely, is formed with
It imitates surface covering to invade with space, occupies suitable flame retardant activity position, and increase trap quantity, improve electric charge stream
It is dynamic, average breakdown strength is increased, the service life for improving artificial stone is conducive to.Therefore, the artificial stone of the application can both carry
High service life, ageing-resistant, impact resistance, intensity is high, and can also keep preferable flame retardant effect, greatly improves LOI loss on ignitions
Index.
The artificial stone of the present invention due to using nano-perovskite oxide material for the first time, using its advantage space structure, and
With UIO Material claddings, a part can generate more inorganic nano flame-retardant composition, another part can utilize space omission with
The skeleton structure of UIO, optimizes the carbon-forming performance of polymer material, improves LOI indexes, and the organic backbone in UIO can be with
Polyene ester material is further compound, is conducive to comprehensive covering of fire proofing, greatly improves flame retardant property.It can substantially reduce old
Change, improves the high temperature resistant, use intensity and resistance to flame retardant property of artificial stone.
The application has studied including composite L axSr1-xCoO3With metal organic framework UIO-66 to talcum powder/quartz/
The fire-retardant and mechanical property of phenolic resin composite can by having limited oxygen index, vertical combustion and mechanical property tests to measure
Know that composite material combination property is excellent, performance stabilization, oxygen index (OI) height, good flame retardation effect, effect are lasting, cheap.By not waving
Hair, smog are small, non-toxic, which has fire-retardant, suppression cigarette and the function of reducing toxic gas concurrently, is a kind of no environment
Polluting fire proofing has prospects for commercial application.
Specific implementation mode
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
（1）Prepare compound La0.7Sr0.3CoO3With UIO-66：
（a）Lanthanum nitrate, cobalt nitrate, strontium nitrate and nitric acid are weighed in proportion, is dissolved in deionized water, and it is molten to be configured to nitrate
Liquid, wherein nitric acid：Metal ion：The molar ratio of water is 1：4:70；It separately weighs citric acid to be dissolved in deionized water, is configured to lemon
The molar ratio of acid solution, wherein citric acid and water is 6:40；
（b）Mixed nitrate solution is heated to 70 DEG C, stirs lower dropwise addition citric acid solution, citric acid amount and the gold of addition
The molar ratio for belonging to ion is 1:1；Nitrate solution and citric acid solution be sufficiently mixed uniformly after with concentrated ammonia liquor tune pH value of solution to 7；
Gel is obtained after being kept for 2 hours at 80 DEG C；
（c）Gained gel is dried into xerogel at 100 DEG C, is then handled 1 hour at 400 DEG C, obtains nanometer calcium titanium
Mine catalyst La0.7Sr0.3CoO3。
It is prepared by UIO-66：0.932gZrC1 is weighed respectively4With 1.32 g terephthalic acid (TPA)s, in polytetrafluoroethylliner liner,
24 mL DMF solvents are added to be dissolved, 0.665 mL concentrated hydrochloric acids are then added, are uniformly mixed, are ultrasonically treated 5 min, it will be interior
Courage seal, be put into baking oven in 120 DEG C heating reaction 16h, then reduce the temperature to room temperature, by mixture after reaction from
The heart obtains white precipitate, as UiO-66 in centrifugation bottom of the tube.
（2）By 70 parts of talcum powder, 50 parts of phenolic resin, 6 parts of boron trifluoride, 10 parts of white carbon, 25 parts of perlite powder,
What 5 parts of melamine, 5 parts of triethyl phosphate, 5 parts of hydroxyapatite, 5 parts of mica sheet, 50 parts of quartz and above-mentioned steps obtained
LaxSr1-xCoO3 5 parts of 10 parts, UIO-66 mixing, pour into homogenizer, first 1000 revs/min of speed are used to stir at room temperature
It mixes 30 minutes, 30min is then stirred with 3000 revs/min of speed at 50 DEG C, the batch mixing stirred evenly is discharged, is uniformly taped against
On making sheet mold, making sheet mold is then placed in vacuum environment dry solidification at 50 DEG C and is molded, after being removed from the molds solidification
Artificial stone blank, fixed thick, polishing, polishing treatment fire retardant man-made stone are carried out to blank.
Embodiment 2
（1）Prepare compound La0.8Sr0.2CoO3With UIO-66：
（a）Lanthanum nitrate, cobalt nitrate, strontium nitrate and nitric acid are weighed in proportion, is dissolved in deionized water, and mixed nitrate is configured to
Salting liquid, wherein nitric acid：Metal ion：The molar ratio of water is 2：4:70；It separately weighs citric acid to be dissolved in deionized water, be configured to
The molar ratio of citric acid solution, wherein citric acid and water is 8:40；
（b）Mixed nitrate solution is heated to 70 DEG C, stirs lower dropwise addition citric acid solution, citric acid amount and the gold of addition
The molar ratio for belonging to ion is 1:2；Nitrate solution and citric acid solution be sufficiently mixed uniformly after with concentrated ammonia liquor tune pH value of solution to 7；
Gel is obtained after being kept for 3 hours at 75 DEG C；
（c）Gained gel is dried into xerogel at 100 DEG C, is then handled 1 hour at 350 DEG C, obtains nanometer calcium titanium
Mine catalyst La0.8Sr0.2CoO3。
It is prepared by UIO-66：0.932g ZrC14 and 1.32 g terephthalic acid (TPA)s are weighed respectively, in polytetrafluoroethylliner liner,
24 mL DMF solvents are added to be dissolved, 0.665 mL concentrated hydrochloric acids are then added, are uniformly mixed, are ultrasonically treated 5 min, it will be interior
Courage seal, be put into baking oven in 120 DEG C heating reaction 16h, then reduce the temperature to room temperature, by mixture after reaction from
The heart obtains white precipitate, as UiO-66 in centrifugation bottom of the tube.
（2）By 80 parts of talcum powder, 55 parts of phenolic resin, 8 parts of boron trifluoride, 15 parts of white carbon, 28 parts of perlite powder,
10 parts of melamine, 10 parts of triethyl phosphate, 10 parts of hydroxyapatite, 10 parts of mica sheet, 60 parts of quartz and above-mentioned steps obtain
LaxSr1-xCoO3 8 parts of 15 parts, UIO-66 mixing, pour into homogenizer, first use 1000 revs/min of speed at room temperature
Then stirring 30 minutes stirs 30min at 50 DEG C with 3000 revs/min of speed, the batch mixing stirred evenly is discharged, and uniformly spreads
Onto making sheet mold, making sheet mold is then placed in vacuum environment dry solidification at 55 DEG C and is molded, solidification is removed from the molds
Artificial stone blank afterwards carries out fixed thick, polishing to blank, polishing treatment obtains fire retardant man-made stone.
Embodiment 3
（1）Prepare compound La0.9Sr0.1CoO3With UIO-66：
（a）Lanthanum nitrate, cobalt nitrate, strontium nitrate and nitric acid are weighed in proportion, is dissolved in deionized water, and it is molten to be configured to nitrate
Liquid, wherein nitric acid：Metal ion：The molar ratio of water is 1：3：70；It separately weighs citric acid to be dissolved in deionized water, is configured to lemon
The molar ratio of acid solution, wherein citric acid and water is 5:40；
（b）Mixed nitrate solution is heated to 80 DEG C, stirs lower dropwise addition citric acid solution, citric acid amount and the gold of addition
The molar ratio for belonging to ion is 1:1；Nitrate solution and citric acid solution be sufficiently mixed uniformly after with concentrated ammonia liquor tune pH value of solution to 7；
Gel is obtained after being kept for 2 hours at 80 DEG C；
（c）Gained gel is dried into xerogel at 90 DEG C, is then handled 1 hour at 400 DEG C, obtains nano-perovskite
Catalyst La0.9Sr0.1CoO3。
It is prepared by UIO-66：0.932g ZrC14 and 1.32 g terephthalic acid (TPA)s are weighed respectively, in polytetrafluoroethylliner liner,
24 mL DMF solvents are added to be dissolved, 0.665 mL concentrated hydrochloric acids are then added, are uniformly mixed, are ultrasonically treated 5 min, it will be interior
Courage seal, be put into baking oven in 120 DEG C heating reaction 16h, then reduce the temperature to room temperature, by mixture after reaction from
The heart obtains white precipitate, as UiO-66 in centrifugation bottom of the tube.
（2）By 90 parts of talcum powder, 60 parts of phenolic resin, 10 parts of boron trifluoride, 20 parts of white carbon, 30 parts of perlite powder,
15 parts of melamine, 15 parts of triethyl phosphate, 15 parts of hydroxyapatite, 15 parts of mica sheet, 70 parts of quartz and above-mentioned steps obtain
LaxSr1-xCoO310 parts of 20 parts, UIO-66 mixing, pour into homogenizer, first use 1000 revs/min of speed at room temperature
Degree stirring 30 minutes, then stirs 30min at 50 DEG C with 3000 revs/min of speed, the batch mixing stirred evenly is discharged, uniformly
It is taped against on making sheet mold, making sheet mold is then placed in 65 DEG C of dry solidification moldings in vacuum environment, is removed from the molds solidification
Artificial stone blank afterwards carries out fixed thick, polishing to blank, polishing treatment obtains fire retardant man-made stone.
Comparative example 1
It is added without nano-perovskite LaxSr1-xCoO3, other experiment parameters are the same as embodiment 1.
Comparative example 2
UIO materials are added without, other experiment parameters are the same as embodiment 1.
Comparative example 3
The La of the present invention is replaced using concave convex rodxSr1-xCoO3, other experiment parameters are the same as embodiment 1.
Comparative example 4
The UIO-66 of the present invention is replaced using 4A molecular sieves, other experiment parameters are the same as embodiment 1.
Specific detection
Detect the tensile strength (σ t/MPa) of above-mentioned anti-aging artificial stone, elongation at break (δ/ %), carbon left, hardness,
Then above-mentioned anti-aging artificial stone is carried out hot air aging by LOI indexes all over the world by 200 DEG C × 30, then detect tensile strength
Conservation rate (E1/ %) and elongation at break conservation rate (E2/ %), concrete outcome is shown in Table 1.
The each Testing index of 1 artificial stone material of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Carbon residue, wt% | 21 | 22 | 24 | 5.5 | 7.6 | 3.8 | 6.5 |
| Hardness, ShoreA | 90 | 90 | 89 | 78 | 71 | 72 | 69 |
| Tensile strength, MPa | 50 | 52 | 49 | 42 | 39 | 43 | 42 |
| Elongation at break % | 550 | 530 | 540 | 390 | 395 | 342 | 370 |
| LOI | 35.2 | 35.3 | 38.3 | 19.3 | 14.2 | 17.9 | 16.7 |
| 200 DEG C × 30 days, LOI | 33.5 | 34.5 | 33.2 | 14.8 | 11.8 | 10.9 | 12.8 |
| 200 DEG C × 30 days, E1/ % | 96.5 | 93.9 | 94.0 | 66.5 | 64.0 | 65 | 70.4 |
| 200 DEG C × 30 days, E2/ % | 90.3 | 90.7 | 91.2 | 60.7 | 60.9 | 52.7 | 57.6 |
There are the above results to can be seen that LaxSr1-xCoO3Artificial stone is advantageously reduced with metal organic framework UIO-66 modifications
Density, improve the heat resistance and intensity of artificial stone, reduce the ageing time of artificial stone, improve LOI indexes, there is good resistance
Combustion property can be kept under high temperature action for a long time（200 DEG C × 30 days）It is non-degradable, and by for a long time（200 DEG C × 30 days）
Still have higher LOI indexes, flame retardant property still preferable.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those skilled in the art within the technical scope disclosed by the invention, can without the variation that creative work is expected or
It replaces, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Subject to fixed protection domain.
Claims (5)
1. a kind of preparation method of the fire retardant man-made stone comprising nano-perovskite oxide, which is characterized in that specific preparation process
Including：
（1）Prepare LaxSr1-xCoO3With UIO-66,
（2）By 70-90 parts of talcum powder, 50-60 parts of phenolic resin, 6-10 parts of boron trifluoride, 10-20 parts of white carbon, crushed crude pearlite
25-30 parts last, 5-15 parts of melamine, 5-15 parts of triethyl phosphate, 5-15 parts of hydroxyapatite, 5-15 parts of mica sheet, quartz
50-70 parts and step（1）Obtained LaxSr1-xCoO3 5-10 parts of 10-20 parts, UIO-66 mixing, pour into homogenizer, room
It first uses 1000 revs/min of speed to stir under temperature 30 minutes, 30min is then stirred with 3000 revs/min of speed at 50 DEG C,
The batch mixing stirred evenly is discharged, is uniformly taped against on making sheet mold, making sheet mold is then placed in dry solidification in vacuum environment
Molding, the artificial stone blank being removed from the molds after solidification carries out fixed thick, polishing to blank, polishing treatment obtains fire retardant man-made
Stone；Wherein nano-perovskite oxide LaxSr1-xCoO3In, 0.6<x<1.
2. preparation method as described in claim 1, which is characterized in that step（1）Middle nano-perovskite LaxSr1-xCoO3System
Preparation Method is：
（a）Lanthanum nitrate, cobalt nitrate, strontium nitrate and nitric acid are weighed in proportion, is dissolved in deionized water, and it is molten to be configured to mixed nitrate
Liquid, wherein nitric acid：Metal ion：The molar ratio of water is（1-4）：（2~4）：70；It separately weighs citric acid to be dissolved in deionized water, match
Citric acid solution is made, the molar ratio of wherein citric acid and water is（4~8）：40；
（b）Nitrate solution is heated to 70 ~ 80 DEG C, stir it is lower be added dropwise citric acid solution, the citric acid amount of addition and metal from
The molar ratio of son is 1:1~1:2；Nitrate solution and citric acid solution be sufficiently mixed uniformly after with concentrated ammonia liquor tune pH value of solution to 7；
Gel is obtained after being kept for 2 ~ 3 hours at 75 ~ 80 DEG C；
（c）Gained gel is dried into xerogel at 90 ~ 100 DEG C, then handles 0.5 ~ 1 hour, is received at 350 ~ 400 DEG C
Rice perovskite oxide La1-XSrXCoO3。
3. preparation method as claimed in claim 1 or 2, which is characterized in that step（1）The preparation method of middle UIO-66 is：Point
Also known as take 0.932g ZrC14With 1.32 g terephthalic acid (TPA)s, in polytetrafluoroethylliner liner, be added 24 mL DMF solvents by its
Dissolving, is then added 0.665 mL concentrated hydrochloric acids, is uniformly mixed, and is ultrasonically treated 5 min, liner is sealed, is put into baking oven in 120
DEG C heating reaction 16h, then reduce the temperature to room temperature, by centrifuge to mixture after reaction, centrifuge bottom of the tube obtain white
Precipitation, as UiO-66.
4. preparation method as described in claim 1, which is characterized in that step（2）Middle dry solidification forming temperature is 50-65
℃。
5. preparation method as described in claim 1, which is characterized in that nano-perovskite oxide LaxSr1-xCoO3Average grain
Diameter is 20-85nm.
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| CN101269839A (en) * | 2007-03-22 | 2008-09-24 | 天津市环科机动车尾气催化净化技术有限公司 | Preparation technique for perovskite type rare earth manganate with lemon acid method |
| CN101791575A (en) * | 2010-03-23 | 2010-08-04 | 上海师范大学 | Preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals |
| CN104478289A (en) * | 2014-12-15 | 2015-04-01 | 田忠和 | Fireproof and pressure-resistant artificial quartz stone plate and preparation method thereof |
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| CN105457647B (en) * | 2015-12-10 | 2021-02-26 | 复旦大学 | Nano perovskite type catalyst La1-XBiXCoO3And preparation method and application thereof |
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| CN101269839A (en) * | 2007-03-22 | 2008-09-24 | 天津市环科机动车尾气催化净化技术有限公司 | Preparation technique for perovskite type rare earth manganate with lemon acid method |
| CN101791575A (en) * | 2010-03-23 | 2010-08-04 | 上海师范大学 | Preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals |
| CN104478289A (en) * | 2014-12-15 | 2015-04-01 | 田忠和 | Fireproof and pressure-resistant artificial quartz stone plate and preparation method thereof |
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