CN105907034B - One kind includes nano-perovskite oxide M TiO3Fire retardant man-made stone preparation method - Google Patents
One kind includes nano-perovskite oxide M TiO3Fire retardant man-made stone preparation method Download PDFInfo
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- C08K5/00—Use of organic ingredients
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Abstract
Include nano-perovskite oxide M TiO the present invention relates to one kind3Fire retardant man-made stone preparation method, nano-perovskite oxide is jointly added to metal organic framework ZIF 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
Include nano-perovskite oxide M TiO the present invention relates to one kind3Fire retardant man-made stone preparation method, belong to and build
Build 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
Include nano-perovskite oxide the present invention provides one kind for many deficiencies existing for existing artificial stone
MTiO3Fire retardant man-made stone preparation method, specific preparation process includes：
（1）Prepare MTiO3With ZIF-90,
（2）By 70-90 parts of talcum powder, 50-60 parts of phenolic resin, 6-10 parts of acid anhydrides, 10-20 parts of white carbon, crushed crude pearlite
25-30 parts last, 5-15 parts of dicyandiamide, 5-15 parts of triethyl phosphate, 5-15 parts of hydroxyapatite, 5-15 parts of mica sheet, quartz 50-
70 parts of MTiO obtained with above-mentioned steps3 5-10 parts of 10-20 parts, ZIF-90 mixing, pour into homogenizer, first adopt at room temperature
It is stirred 30 minutes with 1000 revs/min of speed, 30min is then stirred with 3000 revs/min of speed at 50 DEG C, stirring is equal
Even batch mixing discharge, is uniformly taped against on making sheet mold, and making sheet mold, which is then placed in dry solidification in vacuum environment, is molded, from mould
The artificial stone blank after solidification is taken out in tool, fixed thick, polishing is carried out to blank, polishing treatment obtains fire retardant man-made stone；Wherein receive
Rice perovskite oxide MTiO3Middle M=Ba, Sr, Ca.
Wherein, nano-perovskite oxide M TiO3Preparation method be：
0.05-0.5mol/l tetrabutyl titanates are dissolved in 10ml glycol monoethyl ethers, ultrasonic disperse stirs evenly, and adds
Entering 25wt% ammonium hydroxide, obtains the hydroxide precipitation of titanium, then deionization washing is added KOH aqueous solutions, stirs 10-20 minutes,
It is uniformly mixed, moves into hydrothermal crystallizing kettle, react 1-4h at 140-200 DEG C, after reaction, wash, it is dry, obtain nano barium titanate
Salt template；
In Nano titanate template, 15-20mlM (NO are added dropwise3)2Solution and 10-15ml tetramethylammonium hydroxide are water-soluble
Liquid stirs 2h, after being sufficiently mixed uniformly, then carries out 180-220 DEG C of hydro-thermal reaction 1-4h, postcooling precipitation, it is final to obtain
Product washed respectively with deionized water, methanol.
Wherein, the ZIF-90 the specific steps are：By Zn (NO3)2·6H2O (2.1mmol) and imidazoles -2- formaldehyde ICA
(3.0mmol) is dissolved in the reaction solution that stirs evenly and will obtain in the DMF of 30mL and is transferred to volume as 40mL polytetrafluoroethylene (PTFE) lining
In reaction kettle 18h cooled to room temperatures are reacted at 100 DEG C.
Wherein, step（2）Middle dry solidification forming temperature is 50-65 DEG C, preferably 55-60 DEG C.
Wherein, nano-perovskite oxide M TiO3：The mass ratio of ZIF is 2-4：1, preferably 2:1.
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.
Dicyandiamide has the advantages that Halogen, low toxicity, low cigarette, and nitrogenous flame ratardant is preferable in the flame retardant effect of polyester plastics, especially
It is combined with phosphorus flame retardant, and Intumscent Flame Retardant System can be formed, and by the synergistic effect of the two, can be greatly improved poly-
The flame retardant effect of enester hydrocarbon artificial stone.The application uses dicyandiamide and is applied in combination with triethyl phosphate, hydroxyapatite, and adjusts
The ratio of whole three makes three play synergistic effect, forms Intumscent Flame Retardant System, experiments have shown that, three（Dicyandiamide：Phosphoric acid
Triethyl：Hydroxyapatite）Best mass ratio is 1:1:1, flame retardant effect can be greatly improved.Nano inorganic oxide is resistance
The good selection of agent, such as nano magnesia are fired, nano zine oxide etc. all can serve as the addition of nano inorganic oxide fire retardant
Into polyene ester material.Due to nano effect, Preparing Organic-inorganic Nano Hybrid Material has more conventional polymer/filler compound
Object is incomparable a little, for example density is small, high mechanical strength, inspiratory and permeability, especially heat resistance and fire-retardant
Property can be greatly improved.Further, it is multiple to study the clays class phyllosilicate nanos such as concave convex rod, montmorillonite by some scholars
The flame retardant property of condensation material, above-mentioned inorganic material have different degrees of flame retardant effect.Perovskite structure oxide ABO3 has
Unique optics, electricity and magnetic performance are widely used in terms of biological agent ceramics, have thermal stability 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.There is presently no adopt
Use nano-perovskite material that structure is more excellent or similar polymetallic metal composite oxide as fire proofing.
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 ZIF-90, 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, ZIF-90 have good water-resistance, acid-resisting.
Therefore, the application is soundd out using ZIF-90 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 ZIFS, 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 M TiO for the first time3As inorganic nano flame retardant constituent, it is added to polyene
In ester material, due to the addition of nano-perovskite, thus it is possible to vary transfer ways of the carrier in medium reduce trap level,
Carrier is set to be easy to, along transporting perpendicular to thickness direction, the injection of carrier through-thickness and space charge effectively be inhibited to exist
Accumulation semi-conductive layers in medium weaken extra electric field to a certain extent on thickness of sample direction, reduce semi-conductive layer
With the field strength at interfacial dielectric layer, reduce the space charge amount of cathode injection, a small amount of space of final residual in sample after short circuit
Charge reduces the aggregation of charge, improves the electricity saving performance of material, improves anti-aging, the high temperature resistance of artificial stone, rises
To efficient fire-retardant purpose.
The application polyalkenylesters main material is ternary material：Talcum powder, quartz, phenolic resin mixing, composite high-molecular type
It expands, is conducive to the complementary structure of various high molecular materials, being in direct contact for composite flame-proof agent material and polyalkenylesters is close to tie
It closes, forms active surface covering and invaded with space, occupy suitable flame retardant activity position, and increase trap quantity, improve
Charge flowing, increases average breakdown strength, is conducive to the service life for improving artificial stone.Therefore, the artificial stone of the application
Both service life can be improved, ageing-resistant, impact resistance, intensity is high, and can also keep preferable flame retardant effect, greatly improves
LOI loss on ignition indexes.
The fire retardant man-made stone of the present invention is tied due to using nano-perovskite oxide material for the first time using its advantage space
Structure, and with ZIF Material claddings, a part can generate more inorganic nano flame-retardant composition, another part can utilize space
The vacant skeleton structure with ZIF optimizes the carbon-forming performance of polymer material, improves LOI indexes, and the organic backbone in ZIF
Can be further compound with polyene ester material, be conducive to comprehensive covering of fire proofing, greatly improve flame retardant property.It can be significantly
Aging is reduced, the high temperature resistant, use intensity and resistance to flame retardant property of artificial stone are improved.
The application has studied including composite material MTiO3With ZIF-90 to talcum powder/quartz/phenolic resin composite
Fire-retardant and mechanical property, by thering are limited oxygen index, vertical combustion and mechanical property tests to measure, it is known that composite material combination property
Excellent, performance stabilization, oxygen index (OI) height, good flame retardation effect, effect are lasting, cheap.It is non-toxic by non-volatile, smog is small, it should
Composite flame-proof material has fire-retardant, suppression cigarette and the function of reducing toxic gas concurrently, and being a kind of non-environmental-pollution fire proofing has work
Industry application prospect.
Specific implementation mode
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
（1）Prepare BaTiO3With ZIF-90：
(a) Nano titanate template is prepared：0.1mol/l tetrabutyl titanates are dissolved in 10ml glycol monoethyl ethers, ultrasound
Dispersion, stirs evenly, and 25% ammonium hydroxide is added, and obtains the hydroxide precipitation of titanium, deionization washing.Then 1mol/lKOH water is added
Solution stirs 10-20 minutes, is uniformly mixed, and moves into hydrothermal crystallizing kettle, reacts 1-4h at 140-200 DEG C.After reaction, it washes
It washs, it is dry, obtain Nano titanate template；
In 2g Nano titanate nano-forms, the barium nitrate solution and 10ml concentration of a concentration of 0.2mol/l of 15ml is added dropwise
For the tetramethylammonium hydroxide aqueous solution of 0.1mol/l, 2h is stirred, after being sufficiently mixed uniformly, then carries out 180-220 DEG C of hydro-thermal
React 1-4h, postcooling precipitation.The product finally obtained is washed with deionized water, methanol respectively.Obtained BaTiO3Oxidation
Object average grain diameter is 45-55nm.
(b) prepared by ZIF-90：By Zn (NO3)2 6H2O (2.1mmol) and imidazoles -2- formaldehyde ICA (3.0mmol) are dissolved in
Stirred evenly in the DMF of 30mL the reaction solution that will be obtained be transferred to volume be 40mL teflon lineds reaction kettle exist
It is spare that 18h cooled to room temperatures are reacted at 100 DEG C.
（2）By 70 parts of talcum powder, 50 parts of phenolic resin, 6 parts of acid anhydrides, 10 parts of white carbon, 25 parts of perlite powder, double cyanogen
The La that 5 parts of amine, 5 parts of triethyl phosphate, 5 parts of hydroxyapatite, 5 parts of mica sheet, 50 parts of quartz and above-mentioned steps obtainxSr1- xCoO3 5 parts of 10 parts, ZIF-90 mixing, pour into homogenizer, first use 1000 revs/min of speed to stir 30 points at room temperature
Then clock stirs 30min at 50 DEG C with 3000 revs/min of speed, the batch mixing stirred evenly is discharged, making sheet mould is uniformly taped against
On tool, making sheet mold is then placed in vacuum environment dry solidification at 50 DEG C and is molded, is removed from the molds artificial after solidification
Stone blank carries out fixed thick, polishing, polishing treatment fire retardant man-made stone to blank.
Embodiment 2
(1）Prepare SrTiO3With ZIF-90：
(a) Nano titanate template is prepared：0.3mol/l tetrabutyl titanates are dissolved in 10ml glycol monoethyl ethers, ultrasound
Dispersion, stirs evenly, and 25wt% ammonium hydroxide is added, and obtains the hydroxide precipitation of titanium, deionization washing.Then 2mol/l is added
KOH aqueous solutions stir 10-20 minutes, are uniformly mixed, and move into hydrothermal crystallizing kettle, react 1-4h at 140-200 DEG C.Reaction terminates
Afterwards, it washs, it is dry, obtain Nano titanate template；
In 2g Nano titanate templates, a concentration of 0.2mol/l strontium nitrate solutions of 20ml are added dropwise and 10ml is a concentration of
0.1mol/l tetramethylammonium hydroxide aqueous solutions stir 2h, after being sufficiently mixed uniformly, then carry out 200 DEG C of hydro-thermal reaction 4h, it
Postcooling precipitates.The product finally obtained is washed with deionized water, methanol respectively.The size of product SrTiO3 is 40-60nm.
(b) prepared by ZIF-90：By Zn (NO3)2 6H2O (2.1mmol) and imidazoles -2- formaldehyde ICA (3.0mmol) are dissolved in
Stirred evenly in the DMF of 30mL the reaction solution that will be obtained be transferred to volume be 40mL teflon lineds reaction kettle exist
It is spare that 18h cooled to room temperatures are reacted at 100 DEG C.
（2）By 80 parts of talcum powder, 55 parts of phenolic resin, 8 parts of acid anhydrides, 15 parts of white carbon, 28 parts of perlite powder, double cyanogen
What 10 parts of amine, 10 parts of triethyl phosphate, 10 parts of hydroxyapatite, 10 parts of mica sheet, 60 parts of quartz and above-mentioned steps obtained
LaxSr1-xCoO3 8 parts of 15 parts, ZIF-90 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 55 DEG C and is molded, after being removed from the molds solidification
Artificial stone blank, fixed thick, polishing is carried out to blank, polishing treatment obtains fire retardant man-made stone.
Embodiment 3
（1）Prepare CaTiO3With ZIF-90：
(a) Nano titanate template is prepared：0.5mol/l tetrabutyl titanates are dissolved in 10ml glycol monoethyl ethers, ultrasound
Dispersion, stirs evenly, and 25wt% ammonium hydroxide is added, and obtains the hydroxide precipitation of titanium, deionization washing.Then 1mol/lKOH is added
Aqueous solution stirs 10-20 minutes, is uniformly mixed, and moves into hydrothermal crystallizing kettle, reacts 3h at 200 DEG C.After reaction, it washs,
It is dry, obtain Nano titanate template；
In 3g Nano titanate templates, a concentration of 0.5mol/l calcium nitrate solutions of 15ml are added dropwise and 15ml is a concentration of
0.3mol/l tetramethylammonium hydroxide aqueous solutions stir 2h, after being sufficiently mixed uniformly, then carry out 180 DEG C of hydro-thermal reaction 4h, it
Postcooling precipitates.The product finally obtained is washed with deionized water, methanol respectively.Products C aTiO3Average diameter be 35-
55nm。
(b) prepared by ZIF-90：By Zn (NO3)2 6H2O (2.1mmol) and imidazoles -2- formaldehyde ICA (3.0mmol) are dissolved in
Stirred evenly in the DMF of 30mL the reaction solution that will be obtained be transferred to volume be 40mL teflon lineds reaction kettle exist
It is spare that 18h cooled to room temperatures are reacted at 100 DEG C.
（2）By 90 parts of talcum powder, 60 parts of phenolic resin, 10 parts of acid anhydrides, 20 parts of white carbon, 30 parts of perlite powder, double cyanogen
What 15 parts of amine, 15 parts of triethyl phosphate, 15 parts of hydroxyapatite, 15 parts of mica sheet, 70 parts of quartz and above-mentioned steps obtained
LaxSr1-xCoO310 parts of 20 parts, ZIF-90 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 65 DEG C of dry solidification moldings in vacuum environment, after being removed from the molds solidification
Artificial stone blank, fixed thick, polishing is carried out to blank, polishing treatment obtains fire retardant man-made stone.
Comparative example 1
It is added without nano-perovskite MTiO3, other experiment parameters are the same as embodiment 1.
Comparative example 2
ZIF-90 materials are added without, other experiment parameters are the same as embodiment 1.
Comparative example 3
The MTiO of the present invention is replaced using concave convex rod3, other experiment parameters are the same as embodiment 1.
Comparative example 4
The ZIF-90 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% | 20.5 | 21 | 22.1 | 5.4 | 7.6 | 3.7 | 6.5 |
| Hardness, ShoreA | 90 | 90 | 87 | 78 | 70 | 71 | 69 |
| Tensile strength, MPa | 51 | 51 | 49 | 41 | 39 | 43 | 42 |
| Elongation at break % | 555 | 525 | 540 | 3405 | 395 | 342 | 371 |
| LOI | 35.2 | 35.3 | 38.3 | 19.3 | 14.2 | 17.9 | 16.7 |
| 200 DEG C × 30 days, LOI | 31.5 | 34.6 | 33.2 | 14.9 | 12.5 | 12.9 | 12.8 |
| 200 DEG C × 30 days, E1/ % | 95.5 | 93.9 | 94.5 | 66.5 | 64.5 | 65.1 | 70.4 |
| 200 DEG C × 30 days, E2/ % | 91.3 | 91.7 | 91.2 | 61.7 | 60.9 | 52.5 | 57.6 |
There are the above results to can be seen that MTiO3The close of artificial stone is advantageously reduced with metal organic framework ZIF-90 modifications
Degree, improves the heat resistance and intensity of artificial stone, reduces the ageing time of artificial stone, improves LOI indexes, has good fire-retardant
Property, it can keep 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
So 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. one kind includes nano-perovskite oxide M TiO3Fire retardant man-made stone preparation method, which is characterized in that it is specific to prepare
Step includes：
（1）Prepare MTiO3With ZIF-90,
（2）By 70-90 parts of talcum powder, 50-60 parts of phenolic resin, 6-10 parts of acid anhydrides, 10-20 parts of white carbon, perlite powder
25-30 parts, 5-15 parts of dicyandiamide, 5-15 parts of triethyl phosphate, 5-15 parts of hydroxyapatite, 5-15 parts of mica sheet, quartz 50-70
Part and above-mentioned steps（1）Obtained MTiO3 5-10 parts of 10-20 parts, ZIF-90 mixing, pour into homogenizer, first adopt at room temperature
It is stirred 30 minutes with 1000 revs/min of speed, 30min is then stirred with 3000 revs/min of speed at 50 DEG C, stirring is equal
Even batch mixing discharge, is uniformly taped against on making sheet mold, and making sheet mold, which is then placed in dry solidification in vacuum environment, is molded, from mould
The artificial stone blank after solidification is taken out in tool, fixed thick, polishing is carried out to blank, polishing treatment obtains fire retardant man-made stone；Wherein receive
Rice perovskite oxide MTiO3Middle M=Ba, Sr or Ca.
2. preparation method as described in claim 1, which is characterized in that nano-perovskite oxide M TiO3Preparation method be：
0.05-0.5mol/l tetrabutyl titanates are dissolved in 10ml glycol monoethyl ethers, ultrasonic disperse stirs evenly, and is added
25wt% ammonium hydroxide, obtains the hydroxide precipitation of titanium, then deionization washing is added KOH aqueous solutions, stirs 10-20 minutes, mixes
Uniform, immigration hydrothermal crystallizing kettle is closed, 1-4h is reacted at 140-200 DEG C, after reaction, washs, it is dry, obtain Nano titanate
Template；
In Nano titanate template, 15-20mlM (NO are added dropwise3)2Solution and 10-15ml tetramethylammonium hydroxide aqueous solutions, are stirred
Mix 2h, be sufficiently mixed uniformly after, then carry out 180-220 DEG C of hydro-thermal reaction 1-4h, postcooling precipitation, the product finally obtained
It is washed respectively with deionized water, methanol.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the ZIF-90 the specific steps are：It will
2.1mmol Zn(NO3)2 ·6H2O and 3.0mmol imidazoles -2- formaldehyde ICA, which is dissolved in, to stir evenly in the DMF of 30mL and will obtain
Reaction solution be transferred to the reaction kettle that volume is 40mL teflon lineds and react 18h at 100 DEG C and naturally cool to room
Temperature.
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 M TiO3：The mass ratio of ZIF is
2-4：1.
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| CN103044463A (en) * | 2012-12-12 | 2013-04-17 | 中国科学院宁波材料技术与工程研究所 | Method for high-efficiency preparing zeolite imidazole metal organic frame ZIF-90 |
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