CN106007480A - Preparation method of flame-retardant artificial stone containing pleonaste - Google Patents
Preparation method of flame-retardant artificial stone containing pleonaste Download PDFInfo
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- CN106007480A CN106007480A CN201610456408.9A CN201610456408A CN106007480A CN 106007480 A CN106007480 A CN 106007480A CN 201610456408 A CN201610456408 A CN 201610456408A CN 106007480 A CN106007480 A CN 106007480A
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- flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 28
- 239000002969 artificial stone Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 magnesium aluminate Chemical class 0.000 claims abstract description 13
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 12
- 239000010453 quartz Substances 0.000 claims abstract description 7
- 239000011029 spinel Substances 0.000 claims abstract description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910020068 MgAl Inorganic materials 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 238000007711 solidification Methods 0.000 claims description 10
- 230000008023 solidification Effects 0.000 claims description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 8
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 239000010982 man-made stone Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910015900 BF3 Inorganic materials 0.000 claims description 5
- 206010030113 Oedema Diseases 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000002242 deionisation method Methods 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229950000845 politef Drugs 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 3
- 229910001562 pearlite Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000011833 salt mixture Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910026161 MgAl2O4 Inorganic materials 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000010451 perlite Substances 0.000 description 3
- 235000019362 perlite Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000907903 Shorea Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003434 inspiratory effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/0093—Aluminates
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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
- 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
-
- 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
- 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
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention relates to a preparation method of flame-retardant artificial stone containing pleonaste. Nano magnesium aluminate spinel MgAl2O4 has a special structure and can serve as a high-quality inorganic nano oxide material to be added to talcum powder/phenol-formaldehyde resin/quartz, the heat resistance and the strength of the artificial stone are improved, the ageing time of the artificial stone is shortened, the flame-retardant artificial stone can be prevented from being degraded at the high temperature for a long time, a better flame retardant effect can be kept, the quantity of carbon residues is increased, and the LOI (loss on ignition) index is greatly increased.
Description
Technical field
The present invention relates to the preparation method of a kind of fire retardant man-made stone comprising nano magnalium spinelle, belong to construction material neck
Territory.
Background technology
Along with the lifting of people's living standard, the improvement of living conditions, interior decoration industry fast development, fit up building materials
Consumption is very big, and wherein stone material is that one commonly uses most, and one of most basic building materials are widely used in ground, metope and table top
Mat formation.Lithotome cost of winning is high, it is big to pollute, and containing a large amount of naturally occurring radioactive substances, to human health damage relatively
Greatly.Along with the development of Material Field, the performance of artificial stone material is gradually improved, close to being even more than lithotome,
Increasingly accepted by market and user, be widely used in cabinet, bathroom, ground, wall decoration.But current artificial stone
Material yet suffers from that intensity is low, abrasion-resistant surface is poor, flame-proof heat-resistant performance is strong, the shortcoming of surface gloss difference.
Summary of the invention
The many deficiencies existed for existing artificial stone, the invention provides a kind of fire retardant man-made stone containing magnoferrite
Preparation method, prepare in accordance with the following steps:
(1) complex magnoferrite MgAl is prepared2O4；
(2) by Pulvis Talci 70-90 part, phenolic resin 50-60 part, boron trifluoride 6-10 part, white carbon 10-20 part, crushed crude pearlite
End 25-30 part, tripolycyanamide 5-15 part, triethyl phosphate 5-15 part, hydroxyapatite 5-15 part, mica sheet 5-15 part, quartz
The MgAl that 50-70 part, molecular sieve SBA-15 5-10 part and step (1) obtain2O4 10-20 part mixes, and pours homogenizer into,
The speed first using 1000 revs/min under room temperature stirs 30 minutes, then stirs with the speed of 3000 revs/min at 50 DEG C
30min, discharges the batch mixing stirred, is uniformly taped against on making sheet mould, is then placed in vacuum environment by making sheet mould dry
Dry curing molding, is removed from the molds the artificial stone blank after solidification, blank carries out determining thickness, polishing, polishing are hindered
Combustion artificial stone.
Wherein, MgAl in described step (1)2O4Preparation method be: weigh 0.02molMg (NO respectively3)2· 6H2O、
0.04molAl(NO3)3 9H2O is dissolved in 50ml deionization edema, joins to obtain mixing salt solution, takes 0.04molNa2CO3、
0.06molNaOH is dissolved in 50ml deionized water, the most quickly stirs, and saline solution is added aqueous slkali, makes pH be maintained at 9-11,
Mix homogeneously, filters precipitation, and deionized water is washed till neutrality, dries 8-10h, then at 800-1000 DEG C in 80-100 DEG C of baking oven
Muffle kiln roasting 4-6h.
Wherein, the preparation process of described SBA-15 molecular sieve is: under conditions of 35-40 DEG C, by three block surface activity
Agent P123 is dissolved in appropriate amount of deionized water, is added thereto to tetraethyl orthosilicate (TEOS), hydrochloric acid (HCl), the stirring of continuing vigorous ground
24h, loads 100-180 DEG C of crystallization 24h in politef bottle, is filtered, washed and dried, and finally calcines 5-8h at 550 DEG C, so
After be filtered, washed and dried, the white powder obtained is SBA-15, and the mol ratio of each raw material is about TEOS:P123:HCl:
H2O=1:0.017:5.88:136.
Wherein, in step (2), dry solidification forming temperature is 50-65 DEG C, preferably 55-60 DEG C.
Wherein, magnesium aluminate spinel mean diameter is 20-65nm, preferably 25-45nm.
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, hydroxyapatite
Preferable Deng the flame retardant effect of phosphorus series compound, because the Metaphosphoric acid generated during burning can be grouped to stable poly state, become combustion
Burn the protective layer of point, can completely cut off and be fired contacting of thing and oxygen.The phosphoric acid and the poly-Metaphosphoric acid that generate are the most all strong acid, have the strongest
Dehydration property, it is possible to make polymer dehydration carbonization, and form charring layer at polymer surfaces, reach starvation and stop burning
Purpose.
Tripolycyanamide has Halogen, low toxicity, the advantage of low cigarette, and nitrogenous flame ratardant is preferable at the flame retardant effect of polyester plastics,
Especially be combined with phosphorus flame retardant, Intumscent Flame Retardant System can be formed, by the synergism of the two, can be greatly improved
The flame retardant effect of polyalkenylesters hydrocarbon artificial stone.The application have employed tripolycyanamide and is applied in combination with triethyl phosphate, hydroxyapatite,
And adjust the ratio of three, and making three play synergism, form Intumscent Flame Retardant System, test shows, three's (melamine
Amine: triethyl phosphate: hydroxyapatite) optimal mass ratio is 1:1:1, and 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. can serve as nano inorganic oxide resistance
Combustion agent joins in polyalkenylesters material.Due to nano effect, Preparing Organic-inorganic Nano Hybrid Material have more conventional polymer/
Filler compound is incomparable a little, and such as density is little, mechanical strength is high, inspiratory and permeability, the most heat-resisting
Property and anti-flammability can be greatly improved.Further, also there are the clay class laminar silicic acids such as scholar's research attapulgite, montmorillonite
The fire resistance of salt nano composite material, above-mentioned inorganic material all has flame retardant effect in various degree.Perovskite structure oxide
ABO3 has optics, electricity and the magnetic performance of uniqueness, is widely used, has heat stability in terms of biological agent pottery
Good, low cost, can carry out adsorbing oxygen according to the selection of B position, and A, B atom can mention regulation Lattice Oxygen quantity and activity.Mesh
Before the most do not use nano-perovskite material or similar polymetallic metal composite oxide that structure is more excellent as resistance
Combustible material.
The aerial burning of macromolecular compound is the fiercest a kind of oxidation reaction, belongs to chain reaction course.
Combustion process is bred the most active hydroxyl free radical, when hydroxyl free radical and macromolecular compound meet, generates hydrocarbon
Compound free radical and water, in the presence of oxygen, Hydrocarbon radical decomposition, form again new hydroxyl free radical.So
Circulation, makes combustion reaction constantly continue.The mechanism of action of fire retardant is more complicated, comprises many factors, but mainly by adopting
With either physically or chemically stoping burn cycle.
The present invention use first magnesium aluminate spinel as inorganic nano flame retardant constituent, by itself and molecular sieve SBA-15 and point
Spar adds polyene material together, is mixed to form fire-retardant built agent, moreover it is possible to increase further the intensity of complex material, compensate for point
In son sieve material, the defect of flexible difference, forms hard and soft complementation, inorganic material carries out skeletonizing or intercalation, form spatial stability
Structure, controls the migration rate of space charge, improves charge movement speed, is conducive to capture or detrapping, it is to avoid electric charge
Polymerization, thus avoid artificial stone material usually produced problem such as making it aging, inflammable, improve fire resistance, increase intensity, increase
Add carbon left, thus improve LOI index, ageing-resistant.
The artificial stone of the present invention, owing to using dimension stone of magnesia alumina spinel first, utilizes its advantage space structure, and and SBA-
15 molecular sieves are combined, and a part can produce more inorganic nano flame-retardant composition, removes from and is individually added into inorganic nano magnesium oxide
Deng inorganic anti-flaming material, another part can utilize the vacant framing structure with SBA-15 molecular sieve in space, aggregation thing material
The carbon-forming performance of material, improves LOI index, and the organic backbone in SBA-15 molecular sieve can be multiple further with polyene material
Closing, beneficially comprehensive covering of fire proofing, is greatly improved fire resistance.Can be substantially reduced aging, improve the resistance to of artificial stone
High temperature, use intensity and resistance to fire resistance.
The application have studied and includes composite MgAl2O4With the molecular sieve SBA-15 fire-retardant and power to quartz composite
Learn performance, by having limited oxygen index, vertical combustion and mechanical property tests to measure, it is known that composite material combination property is excellent, property
Energy is stable, oxygen index (OI) height, good flame retardation effect, effect are lasting, cheap;By non-volatile, smog is little, avirulence, this compound resistance
Combustible material have concurrently fire-retardant, press down cigarette and reduce the function of toxic gas, be that a kind of non-environmental-pollution fire proofing has commercial Application
Prospect.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further detailed explanation.
Embodiment 1
(1) complex magnoferrite MgAl is prepared2O4:
(a)MgAl2O4Preparation: weigh 0.02molMg (NO respectively3)2· 6H2O、0.04molAl(NO3)3 ·9H2O is dissolved in
50ml deionization edema, joins to obtain mixing salt solution, takes 0.04molNa2CO3,0.06molNaOH and is dissolved in 50ml deionized water,
The most quickly stirring, saline solution is added aqueous slkali, make PH be maintained at 9-11, mix homogeneously, precipitation filtered, deionization is washed
To neutral.80 DEG C of baking ovens are dried 8h.Then at 800 DEG C of Muffle kiln roasting 4-6h.
B prepared by () SBA-15: under conditions of 40 DEG C, three block surface activating agent P123 are dissolved in appropriate amount of deionized water,
It is added thereto to tetraethyl orthosilicate (TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, load in politef bottle 120
DEG C crystallization 24h, is filtered, washed and dried, and finally calcines 6h at 550 DEG C, is then filtered, washed and dried, the white powder obtained
End is SBA-15, standby；
(2) by Pulvis Talci 70 parts, 50 parts of phenolic resin, boron trifluoride 6 parts, white carbon 10 parts, perlite powder 25 parts, trimerization
Cyanamide 5 parts, triethyl phosphate 5 parts, hydroxyapatite 5 parts, mica sheet 5 parts, 50 parts of quartz, molecular sieve SBA-15 5 parts and above-mentioned
The MgAl that step obtains2O4 10 parts of mixing, pour homogenizer into, first use the speed stirring 30 of 1000 revs/min under room temperature
Minute, then stir 30min at 50 DEG C with the speed of 3000 revs/min, the batch mixing stirred is discharged, is uniformly taped against making sheet
On mould, then making sheet mould is placed in vacuum environment dry solidification molding at 50 DEG C, after being removed from the molds solidification
Artificial stone blank, carries out determining thickness, polishing, polishing obtain fire retardant man-made stone to blank.
Embodiment 2
(1) complex magnoferrite MgAl is prepared2O4:
(a)MgAl2O4Preparation: weigh 0.02molMg (NO3) 2 6H2O, 0.04molAl (NO3) 3 9H2O respectively and be dissolved in 50ml
Deionization edema, joins to obtain mixing salt solution, takes 0.04molNa2CO3,0.06molNaOH and is dissolved in 50ml deionized water, then
Quickly stirring, adds aqueous slkali by saline solution, makes PH be maintained at 9-11, mix homogeneously, precipitation is filtered, during deionized water is washed till
Property.100 DEG C of baking ovens are dried 10h.Then at 800 DEG C of Muffle kiln roasting 4h.
B prepared by () SBA-15: under conditions of 40 DEG C, three block surface activating agent P123 are dissolved in appropriate amount of deionized water,
It is added thereto to tetraethyl orthosilicate (TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, load in politef bottle 120
DEG C crystallization 24h, is filtered, washed and dried, and finally calcines 6h at 550 DEG C, is then filtered, washed and dried, the white powder obtained
End is SBA-15, standby；
(2) by Pulvis Talci 80 parts, 55 parts of phenolic resin, boron trifluoride 8 parts, white carbon 15 parts, perlite powder 28 parts, trimerization
Cyanamide 10 parts, triethyl phosphate 10 parts, hydroxyapatite 10 parts, mica sheet 10 parts, quartz 60 parts, molecular sieve SBA-15 8 parts and
The MgAl that above-mentioned steps obtains2O415 parts of mixing, pour homogenizer into, first use the speed of 1000 revs/min to stir under room temperature
Mix 30 minutes, then stir 30min at 50 DEG C with the speed of 3000 revs/min, the batch mixing stirred is discharged, is uniformly taped against
On making sheet mould, then making sheet mould is placed in vacuum environment in 60 DEG C of dry solidification molding, after being removed from the molds solidification
Artificial stone blank, blank carries out determining thickness, polishing, polishing obtain fire retardant man-made stone.
Embodiment 3
(1) complex magnoferrite MgAl is prepared2O4；
(a)MgAl2O4Preparation: weigh 0.02molMg (NO3) respectively2 6H2O、0.04molAl(NO3) 3 9H2O are dissolved in 50ml and go
Ion edema, joins to obtain mixing salt solution, takes 0.04molNa2CO3,0.06molNaOH and is dissolved in 50ml deionized water, the soonest
Speed stirring, adds aqueous slkali by saline solution, makes PH be maintained at 9-11, mix homogeneously, precipitation is filtered, during deionized water is washed till
Property.80 DEG C of baking ovens are dried 10h.Then at 800 DEG C of Muffle kiln roasting 6h.
B prepared by () SBA-15: under conditions of 40 DEG C, three block surface activating agent P123 are dissolved in appropriate amount of deionized water,
It is added thereto to tetraethyl orthosilicate (TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, load in politef bottle 120
DEG C crystallization 24h, is filtered, washed and dried, and finally calcines 6h at 550 DEG C, is then filtered, washed and dried, the white powder obtained
End is SBA-15, standby；
(2) by Pulvis Talci 90 parts, 60 parts of phenolic resin, boron trifluoride 10 parts, white carbon 20 parts, perlite powder 30 parts, trimerization
Cyanamide 15 parts, triethyl phosphate 15 parts, hydroxyapatite 15 parts, mica sheet 15 parts, quartz 70 parts, molecular sieve SBA-15 10 parts
The MgAl obtained with above-mentioned steps2O420 parts of mixing, pour homogenizer into, first use the speed of 1000 revs/min under room temperature
Stir 30 minutes, then stir 30min at 50 DEG C with the speed of 3000 revs/min, the batch mixing stirred is discharged, uniform spreading
On making sheet mould, then making sheet mould is placed in vacuum environment in 65 DEG C of dry solidification molding, is removed from the molds solidification
After artificial stone blank, blank carries out determining thickness, polishing, polishing obtain fire retardant man-made stone.
Comparative example 1
Being added without nano magnalium spinelle, other experiment parameters are with embodiment 1.
Comparative example 2
Being added without SBA-15 material, other experiment parameters are with embodiment 1.
Comparative example 3
Using attapulgite to replace the magnesium aluminate spinel of the present invention, other experiment parameters are with embodiment 1.
Comparative example 4
Using common molecular sieve to replace the SBA-15 of the present invention, other experiment parameters are with embodiment 1.
Concrete detection
Detect the hot strength (σ t/MPa) of above-mentioned aging resistance artificial stone, elongation at break (δ/ %), carbon left, hardness, LOI refer to
Then above-mentioned aging resistance artificial stone is carried out hot air aging through 250 DEG C × 30 by number all over the world, and then detection hot strength keeps
Rate (E1/ %) and elongation at break conservation rate (E2/ %), concrete outcome is shown in Table 1.
Table 1 each Testing index of artificial stone
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Carbon left, wt% | 18.6 | 196 | 20.1 | 1.19 | 2.1 | 4.4 | 1.5 |
| Hardness, ShoreA | 96 | 95 | 95 | 84 | 75 | 76 | 72 |
| Hot strength, MPa | 52 | 50 | 48 | 45 | 35 | 46 | 43 |
| Elongation at break % | 550 | 521 | 500 | 380 | 395 | 420 | 405 |
| LOI | 39.3 | 37.5 | 39.0 | 19.1 | 20.1 | 25.1 | 27.4 |
| 250 DEG C × 30 days, LOI | 33.8 | 34.1 | 33.5 | 14.3 | 11.2 | 10.5 | 12.7 |
| 250 DEG C × 30 days, E1/ % | 97.4 | 95.3 | 97.6 | 77.5 | 72.5 | 73.6 | 80.3 |
| 250 DEG C × 30 days, E2/ % | 90.7 | 90.5 | 94.0 | 62.9 | 61.9 | 62.5 | 70.4 |
There is the above results it can be seen that by adding magnesium aluminate spinel and molecular sieve SBA-15, advantageously reduce insulant
The density of LDPE/EVA/PVC system, improves thermostability and the intensity of insulant, reduces the ageing time of insulant, improve
LOI index, has good anti-flammability, improves carbon left, long-time (250 DEG C × 30 days) under high temperature action can be kept not drop
Solving, and still have higher LOI index through long-time (250 DEG C × 30 days), fire resistance is preferable.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any
Those of ordinary skill in the art in the technical scope that disclosed herein, the change that can expect without creative work or
Replace, all should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Fixed protection domain is as the criterion.
Claims (5)
1. the preparation method of the fire retardant man-made stone containing magnoferrite, it is characterised in that prepare in accordance with the following steps:
(1) complex magnoferrite MgAl is prepared2O4；
(2) by Pulvis Talci 70-90 part, phenolic resin 50-60 part, boron trifluoride 6-10 part, white carbon 10-20 part, crushed crude pearlite
End 25-30 part, tripolycyanamide 5-15 part, triethyl phosphate 5-15 part, hydroxyapatite 5-15 part, mica sheet 5-15 part, quartz
The MgAl that 50-70 part, molecular sieve SBA-15 5-10 part and step (1) obtain2O4 10-20 part mixes, and pours homogenizer into,
The speed first using 1000 revs/min under room temperature stirs 30 minutes, then stirs with the speed of 3000 revs/min at 50 DEG C
30min, discharges the batch mixing stirred, is uniformly taped against on making sheet mould, is then placed in vacuum environment by making sheet mould dry
Dry curing molding, is removed from the molds the artificial stone blank after solidification, blank carries out determining thickness, polishing, polishing are hindered
Combustion artificial stone.
2. preparation method as claimed in claim 1, it is characterised in that MgAl in described step (1)2O4Preparation method be: point
Another name takes 0.02molMg (NO3)2· 6H2O、0.04molAl(NO3)3 9H2O is dissolved in 50ml deionization edema, joins to obtain salt-mixture
Solution, takes 0.04molNa2CO3, 0.06molNaOH be dissolved in 50ml deionized water, the most quickly stir, saline solution added alkali
Solution, makes pH be maintained at 9-11, mix homogeneously, precipitation is filtered, and deionized water is washed till neutrality, dries 8-in 80-100 DEG C of baking oven
10h, then at 800-1000 DEG C of Muffle kiln roasting 4-6h.
3. preparation method as claimed in claim 2, it is characterised in that the preparation process of described SBA-15 molecular sieve is: at 35-
Under conditions of 40 DEG C, three block surface activating agent P123 are dissolved in appropriate amount of deionized water, are added thereto to tetraethyl orthosilicate
(TEOS), hydrochloric acid (HCl), continuing vigorous ground stirring 24h, load 100-180 DEG C of crystallization 24h in politef bottle, filter, wash
Washing and be dried, finally calcine 5-8h at 550 DEG C, be then filtered, washed and dried, the white powder obtained is SBA-15, respectively
The mol ratio of raw material is TEOS:P123:HCl:H2O=1:0.017:5.88:136.
4. preparation method as claimed in claim 1 or 2, it is characterised in that in step (2), dry solidification forming temperature is 50-
65 DEG C, preferably 55-60 DEG C.
5. preparation method as claimed in claim 1, it is characterised in that magnesium aluminate spinel mean diameter is 20-65nm, preferably
25-45nm。
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| CN201810325700.6A CN108483993A (en) | 2016-06-22 | 2016-06-22 | A kind of preparation method of the fire retardant man-made stone containing magnesium aluminate spinel |
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| CN106007480B (en) | 2018-08-07 |
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Denomination of invention: A preparation method of flame retardant artificial stone containing magnesium aluminum spinel Effective date of registration: 20220325 Granted publication date: 20180807 Pledgee: Bank of China Limited Hezhou branch Pledgor: Guangxi Wansheng Stone Industry Co.,Ltd. Registration number: Y2022450000021 |