CN105621440A - Preparation method and application of metal modified MCM-41 molecular screen - Google Patents

Preparation method and application of metal modified MCM-41 molecular screen Download PDF

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Publication number
CN105621440A
CN105621440A CN201610133433.3A CN201610133433A CN105621440A CN 105621440 A CN105621440 A CN 105621440A CN 201610133433 A CN201610133433 A CN 201610133433A CN 105621440 A CN105621440 A CN 105621440A
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metal
molecular sieve
mcm
preparation
modified mcm
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韩志东
姜丽
徐峰
王永亮
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Harbin University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention provides a preparation method and application of a metal modified MCM-41 molecular screen and relates to a preparation method and application of an MCM-41 molecular screen. The problems that an existing IFR intumescent flame retardant and an existing polyethylene material are high in thermal weight loss and thermal release and low in thermal degradation carbon forming are solved. The preparation method includes the steps that firstly, hexadecyl trimethyl ammonium bromide is taken to be dissolved in deionized water, and ammonia water, tartaric acid and a metal modifier are put in a reaction still for a reaction; secondly, a reactant is taken out of the reaction still, washed, subjected to suction filtration and then dried, and a template is removed. According to the application, IFR and the metal modified MCM-41 molecular screen are taken as raw materials and mixed and ground. The preparation method and application have the advantages that the metal modified MCM-41 molecular screen and FIR coordinate to achieve an outstanding fire retardant effect, mass production is easy, and toxicity is avoided. The metal modified MCM-41 molecular screen is used for fire retardant application to the polyethylene material.

Description

The preparation method of a kind of metal-modified MCM-41 molecular sieve and application thereof
Technical field
The present invention relates to the preparation method of a kind of metal-modified MCM-41 molecular sieve and application thereof
Background technology
Mesopore molecular sieve refers to that aperture is between 2��10nm, and pore distribution evenly and has the inorganic porous material of regular pore canal structure. Mesopore molecular sieve is owing to possessing regular pore passage structure, polymer molecular chain can be made to enter in molecular sieve pore passage, restriction molecule chain movement, nano level mesoporous wall itself has good heat insulating ability and barrier, can effectively delay the thermolysis of molecular resin chain in hole and decompose the release of the small-molecule substance generated, thus material thermal resistance is greatly increased, meanwhile, molecular sieve also has good catalytic capability, is a kind of fire retardant of good performance.
Polyethylene is a kind of thermoplastic resin, have without the performance such as low temperature smelly, nontoxic, resistance to, chemical stability be good, producing and life is being widely used, but polyethylene itself is combustion also adjoint a large amount of heat and obnoxious flavour easily, for huge hidden danger has been buried in the use in producing, living, therefore the fire-retardant of it is of great significance with regard to tool. Tradition halogen system is fire-retardant because discharging a large amount of obnoxious flavoures to be replaced by IFR expanding fire retardant, metal oxide fire retardant gradually in burning, but these two kinds of fire retardants also exist certain drawback, and as thermal weight loss is very high, Thermal release height, thermal destruction becomes carbon low.
Summary of the invention
The present invention is in order to solve existing IFR expanding fire retardant and polythene material thermal weight loss height, Thermal release height, the problem that thermal destruction becomes carbon low, it is provided that the preparation method of a kind of metal-modified MCM-41 molecular sieve and application thereof.
The preparation method of the metal-modified MCM-41 molecular sieve of the present invention carries out according to the following steps:
One, getting cetyl trimethylammonium bromide 0.56g��1.1g is dissolved in 18mL��40mL deionized water, add 5mL ammoniacal liquor, 0.4g��0.7g tartrate and 0.4g��0.9g metal modifiers successively, after stirring 0.5h��1.5h, add 3mL��5mL silicon source material, adjust ph to 8��12; Continue to stir 6h��8h, then regulate temperature of reaction kettle to 90 DEG C��120 DEG C reaction 24 hours; Described ammoniacal liquor mass concentration is 20%; The reagent that described adjust ph adopts is sodium hydroxide; Described metal modifiers is iron nitrate or nickelous nitrate etc.; Described silicon source material is tetraethoxy or water glass etc.;
Two, reactant is taken out from reactor, through deionized water wash, take out filter and it is placed in baking oven, dry 5��8 hours at 80 DEG C, then the reactant after oven dry is placed in retort furnace, it is warming up to 500 DEG C��600 DEG C with the temperature rise rate of 3 DEG C/min, it is incubated 3��8 hours, now eliminates template cetyl trimethylammonium bromide, be i.e. obtained metal-modified MCM-41 molecular sieve; Described metal-modified MCM-41 molecular sieve is iron Modified MCM-41 molecular sieve or nickel Modified MCM-41 molecular sieve;
Described utilizing the molecular sieve modified IFR expanding fire retardant of metal-modified MCM-41, concrete grammar carries out according to the following steps:
In mass ratio for (6��3): 1 takes IFR expanding fire retardant and metal-modified MCM-41 molecular sieve as raw material, then the raw material taken is placed in high speed disintegrator and mixes 1min, mixed raw material is placed in planetary ball mill under the rotating speed of 450r/min, grinds 30min, obtain modified IFR expanding fire retardant.
Method of the present invention possesses following useful effect:
1, the present invention exists good cooperative flame retardant effect between metal-modified MCM-41 molecular sieve and IFR expanding fire retardant, after being applied in polythene material, promote catalysis carbon-forming process, reduce thermal polymer degradation speed and combustion heat rate of release, it is more conducive to form stable Char Residues Structure, little without molten drop, the amount of being fuming, after the metal-modified MCM-41 molecular sieve of the present invention, IFR expanding fire retardant and polythene material compound, compared with the polythene material only adding IFR fire retardant, carbon left is increased to 5%��6%; The flame retardant properties of material can be made to have very big lifting; Thermal release peak delays 4 DEG C��5 DEG C compared with pure polythene material, and Heat liberation unit reduces 6MJ/m2��10MJ/m2, thermal destruction speed decline 2KJ/m2��30KJ/m2;
2, metal modified molecular screen is joined in IFR expanding fire retardant by the present invention, facilitate the consistency of IFR expanding fire retardant and polymeric matrix, reduce the add-on of fire retardant, evade the shortcoming of the material mechanical performance decline caused because of adding in a large number of fire retardant.
3, molecular sieve preparation method provided by the present invention and composite material and preparation method thereof, technique is simple, and operational condition is gentle, is easy to a large amount of production, produces without toxic and harmful, environmentally friendly.
4, the present invention is by metallicss such as molecular sieve MCM-41 load iron, nickel, utilizes the carbon effect that is catalyzed into of the modified molecular sieve of iron, nickel, with conventional expanded fire retardant acting in conjunction, obtains thermal degradation performance and the better polythene material of combustionproperty.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of composite polyethylene material PE/IFR/Ni-MCM-41 prepared by embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the nickel modified molecular screen Ni-MCM-41 of nickel-loaded particle prepared by embodiment 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of composite polyethylene material PE/IFR/Fe-MCM-41 prepared by embodiment 2;
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises any reasonable combination between each embodiment.
Embodiment one: the preparation method of a kind of metal-modified MCM-41 molecular sieve of present embodiment, the method realizes according to the following steps:
One, getting cetyl trimethylammonium bromide 0.56g��1.1g is dissolved in 18mL��40mL deionized water, add 5mL ammoniacal liquor, 0.4g��0.7g tartrate and 0.4g��0.9g metal modifiers successively, after stirring 0.5h��1.5h, add 3mL��5mL silicon source material, adjust ph to 8��12; Continue to stir 6h��8h, then regulate temperature of reaction kettle to 90 DEG C��120 DEG C reaction 24 hours;
Two, reactant is taken out from reactor, through deionized water wash, take out filter and it is placed in baking oven, dry 5��8 hours at 80 DEG C, then the reactant after oven dry is placed in retort furnace, it is warming up to 500 DEG C��600 DEG C with the temperature rise rate of 3 DEG C/min, it is incubated 3��8 hours, now eliminates template cetyl trimethylammonium bromide, be i.e. obtained metal-modified MCM-41 molecular sieve; Described metal-modified MCM-41 molecular sieve is iron Modified MCM-41 molecular sieve or nickel Modified MCM-41 molecular sieve.
Method described in present embodiment possesses following useful effect:
1, present embodiment provides molecular sieve preparation method and composite material and preparation method thereof, technique is simple, and operational condition is gentle, is easy to a large amount of production, without toxic and harmful generation, environmentally friendly.
2, present embodiment is by metallicss such as molecular sieve MCM-41 load iron, nickel, utilizes the carbon effect that is catalyzed into of the modified molecular sieve of iron, nickel, with conventional expanded fire retardant acting in conjunction, obtains thermal degradation performance and the better polythene material of combustionproperty.
Embodiment two: present embodiment and embodiment one are the difference is that the ammoniacal liquor mass concentration 20% described in step one. Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment and embodiment one the difference is that: the reagent that the adjust ph described in step one adopts is sodium hydroxide. Other step and parameter are identical with embodiment one.
Embodiment four: present embodiment and embodiment one to three the difference is that: the described metal modifiers described in step one is iron nitrate or nickelous nitrate. It is identical that other step is recorded with the enforcement of any one in parameter and embodiment one to three mode.
Embodiment five: present embodiment and embodiment one to four the difference is that: the described silicon source material described in step one is tetraethoxy or water glass. It is identical that other step is recorded with the enforcement of any one in parameter and embodiment one to four mode.
Embodiment six: present embodiment utilizes the molecular sieve modified IFR expanding fire retardant of metal-modified MCM-41, and concrete grammar carries out according to the following steps:
In mass ratio for (6��3): 1 takes IFR expanding fire retardant and metal-modified MCM-41 molecular sieve as raw material, then the raw material taken is placed in high speed disintegrator and mixes 1min, mixed raw material is placed in planetary ball mill under the rotating speed of 450r/min, grinds 30min, obtain modified IFR expanding fire retardant.
Method described in present embodiment possesses following useful effect:
1, present embodiment exists good cooperative flame retardant effect between metal-modified MCM-41 molecular sieve and IFR expanding fire retardant, after being applied in polythene material, promote catalysis carbon-forming process, reduce thermal polymer degradation speed and combustion heat rate of release, it is more conducive to form stable Char Residues Structure, little without molten drop, the amount of being fuming, after the metal-modified MCM-41 molecular sieve of the present invention, IFR expanding fire retardant and polythene material compound, compared with the polythene material only adding IFR fire retardant, carbon left is increased to 5%��6%; The flame retardant properties of material can be made to have very big lifting; Thermal release peak delays 4 DEG C��5 DEG C compared with pure polythene material, and Heat liberation unit reduces 6MJ/m2��10MJ/m2, thermal destruction speed decline 2KJ/m2��30KJ/m2;
2, metal modified molecular screen is joined in IFR expanding fire retardant by present embodiment, facilitate the consistency of IFR expanding fire retardant and polymeric matrix, reduce the add-on of fire retardant, evade the shortcoming of the material mechanical performance decline caused because of adding in a large number of fire retardant.
The useful effect of the present invention is verified by following examples:
Embodiment 1
One, getting cetyl trimethylammonium bromide 1.1g is dissolved in 25mL deionized water, adds 5mL ammoniacal liquor, 0.5g tartrate and 0.8g metal modifiers successively, after stirring 0.5h, adds 5mL silicon source material, adjust ph to 9; Continue to stir 6h, then regulate temperature of reaction kettle to 100 DEG C reaction 24 hours; Described ammoniacal liquor mass concentration is 20%; The reagent that described adjust ph adopts is sodium hydroxide; Described metal modifiers is nickelous nitrate; Described silicon source material is tetraethoxy;
Two, reactant is taken out from reactor, through deionized water wash, take out filter and it is placed in baking oven, dry 7 hours at 100 DEG C, then the reactant after oven dry is placed in retort furnace, it is warming up to 550 DEG C with the temperature rise rate of 3 DEG C/min, it is incubated 6 hours, now eliminates template cetyl trimethylammonium bromide, be i.e. obtained nickel Modified MCM-41 molecular sieve;
Utilizing the molecular sieve modified IFR expanding fire retardant of nickel Modified MCM-41, concrete grammar carries out according to the following steps:
In mass ratio for 6:1 takes IFR expanding fire retardant and nickel Modified MCM-41 molecular sieve as raw material, then the raw material taken is placed in high speed disintegrator and mixes 1min, mixed raw material is placed in planetary ball mill under the rotating speed of 450r/min, grinds 30min, obtain modified IFR expanding fire retardant.
In order to verify the present embodiment, 7:13 takes modified IFR expanding fire retardant and polyethylene in mass ratio, is then placed in torque rheometer and mixes, the temperature 140 DEG C of described mixing in torque rheometer, rotating speed 80r/min, and mixing time is 10min; , obtain composite polyethylene material PE/IFR/Ni-MCM-41;
The main raw composition of composite polyethylene material PE/IFR/Ni-MCM-41 prepared by the present embodiment and flame retardant properties are as shown in table 1, comparative example is the polythene material adopting unmodified IFR fire retardant to prepare, main raw composition is as shown in table 1, and other step and parameter are identical with embodiment 1; Fig. 1 is the scanning electron microscope (SEM) photograph of the composite polyethylene material PE/IFR/Ni-MCM-41 prepared with embodiment 1 method, and nickel Modified MCM-41 molecular sieve evenly disperses in composite polyethylene material as shown in Figure 1; Fig. 2 is the scanning electron microscope (SEM) photograph of the nickel modified molecular screen Ni-MCM-41 of embodiment 1 nickel-loaded particle; The nickel metallics of uniform loading on MCM-41 molecular sieve can be found out; Comparative example material and embodiment 1 are carried out thermogravimetric analysis, and result is that embodiment 1 material Thermal release peak is delayed, and carbon left increase is comparative example material increase by 5%��6% relatively; Embodiment 1 material Thermal release total amount reduces 35.87MJ/m as shown in Table 12, mass loss rate is reduced to 84.04%.
Table 1
Embodiment 2
One, getting cetyl trimethylammonium bromide 0.73g is dissolved in 18mL deionized water, adds 5mL ammoniacal liquor, 0.6g tartrate and 0.8g metal modifiers successively, after stirring 0.5h, adds 3.1mL tetraethoxy, adjust ph to 9; Continue to stir 6h, then regulate temperature of reaction kettle to 100 DEG C reaction 24 hours; Described ammoniacal liquor mass concentration is 20%; The reagent that described adjust ph adopts is sodium hydroxide; Described metal modifiers is iron nitrate; Described silicon source material is tetraethoxy;
Two, reactant is taken out from reactor, through deionized water wash, take out filter and it is placed in baking oven, dry 7 hours at 100 DEG C, then the reactant after oven dry is placed in retort furnace, it is warming up to 550 DEG C with the temperature rise rate of 3 DEG C/min, it is incubated 6 hours, now eliminates template cetyl trimethylammonium bromide, be i.e. obtained iron Modified MCM-41 molecular sieve;
Utilizing the molecular sieve modified IFR expanding fire retardant of iron Modified MCM-41, concrete grammar carries out according to the following steps:
In mass ratio for 6:1 takes IFR expanding fire retardant and iron Modified MCM-41 molecular sieve as raw material, then the raw material taken is placed in high speed disintegrator and mixes 1min, mixed raw material is placed in planetary ball mill under the rotating speed of 450r/min, grinds 30min, obtain modified IFR expanding fire retardant.
In order to verify the present embodiment, 7:13 takes modified IFR expanding fire retardant and polyethylene in mass ratio, is then placed in torque rheometer and mixes, obtains composite polyethylene material PE/IFR/Fe-MCM-41; The temperature 140 DEG C of described mixing in torque rheometer, rotating speed 80r/min, mixing time is 10min;
Composite polyethylene material PE/IFR/Fe-MCM-41 main raw composition and flame retardant properties prepared by the present embodiment are as shown in table 2, and comparative example is polythene material, and main raw composition is as shown in table 2, and other step and parameter are identical with embodiment 2; Fig. 3 is the scanning electron microscopic picture figure of composite polyethylene material PE/IFR/Fe-MCM-41 prepared by embodiment 2 method, and as shown in Figure 3, iron Modified MCM-41 molecular sieve evenly disperses in composite polyethylene material PE/IFR/Fe-MCM-41; Thermal release total amount reduces 39.68MJ/m than pure polythene material as shown in Table 22, mass loss is reduced to 77.3% by 96.50%.
Table 2
Embodiment 3
One, getting cetyl trimethylammonium bromide 0.56g is dissolved in 40mL deionized water, adds 5mL ammoniacal liquor, 0.6g tartrate and 0.4g metal modifiers successively, after stirring 0.5h, adds 3.4mL tetraethoxy, adjust ph to 9; Continue to stir 11h, then regulate temperature of reaction kettle to 100 DEG C reaction 24 hours; Described ammoniacal liquor mass concentration is 20%; The reagent that described adjust ph adopts is sodium hydroxide; Described metal modifiers is nickelous nitrate; Described silicon source material is tetraethoxy;
Two, reactant is taken out from reactor, through deionized water wash, take out filter and it is placed in baking oven, dry 7 hours at 100 DEG C, then the reactant after oven dry is placed in retort furnace, it is warming up to 550 DEG C with the temperature rise rate of 3 DEG C/min, it is incubated 6 hours, now eliminates template cetyl trimethylammonium bromide, be i.e. obtained nickel Modified MCM-41 molecular sieve;
Utilizing the molecular sieve modified IFR expanding fire retardant of nickel Modified MCM-41, concrete grammar carries out according to the following steps:
In mass ratio for 6:1 takes IFR expanding fire retardant and nickel Modified MCM-41 molecular sieve as raw material, then the raw material taken is placed in high speed disintegrator and mixes 1min, mixed raw material is placed in planetary ball mill under the rotating speed of 450r/min, grinds 30min, obtain modified IFR expanding fire retardant.
In order to verify the present embodiment, 7:13 takes modified IFR expanding fire retardant and polyethylene in mass ratio, is then placed in torque rheometer and mixes, obtains composite polyethylene material PE/IFR/Ni-MCM-41; The temperature 140 DEG C of described mixing in torque rheometer, rotating speed 80r/min, mixing time is 10min;
The main raw composition of composite polyethylene material PE/IFR/Ni-MCM-41 prepared by the present embodiment and flame retardant properties are as shown in table 3, comparative example is polythene material, main raw composition is as shown in table 3, and the composite polyethylene material PE/IFR/Ni-MCM-41 Thermal release total amount that as shown in Table 3 prepared by embodiment 3 reduces 63.54MJ/m than pure polyethylene2, mass loss is reduced to 65.92% by 96.50%.
Table 3

Claims (6)

1. the preparation method of a metal-modified MCM-41 molecular sieve, it is characterised in that the method realizes according to the following steps:
One, getting cetyl trimethylammonium bromide 0.56g��1.1g is dissolved in 18mL��40mL deionized water, add 5mL ammoniacal liquor, 0.4g��0.7g tartrate and 0.4g��0.9g metal modifiers successively, after stirring 0.5h��1.5h, add 3mL��5mL silicon source material, adjust ph to 8��12; Continue to stir 6h��8h, then regulate temperature of reaction kettle to 90 DEG C��120 DEG C reaction 24 hours;
Two, reactant is taken out from reactor, through deionized water wash, take out filter and it is placed in baking oven, dry 5��8 hours at 80 DEG C, then the reactant after oven dry is placed in retort furnace, it is warming up to 500 DEG C��600 DEG C with the temperature rise rate of 3 DEG C/min, it is incubated 3��8 hours, now eliminates template cetyl trimethylammonium bromide, be i.e. obtained metal-modified MCM-41 molecular sieve.
2. the preparation method of a kind of metal-modified MCM-41 molecular sieve according to claim 1, it is characterised in that the ammoniacal liquor mass concentration described in step one is 20%.
3. the preparation method of a kind of metal-modified MCM-41 molecular sieve according to claim 1, it is characterised in that the reagent that the adjust ph described in step one adopts is sodium hydroxide.
4. the preparation method of a kind of metal-modified MCM-41 molecular sieve according to claim 1, it is characterised in that the described metal modifiers described in step one is iron nitrate or nickelous nitrate.
5. the preparation method of a kind of metal-modified MCM-41 molecular sieve according to claim 1, it is characterised in that the described silicon source material described in step one is tetraethoxy or water glass.
6. the application of metal-modified MCM-41 molecular sieve as claimed in claim 1, it is characterised in that utilizing the molecular sieve modified IFR expanding fire retardant of metal-modified MCM-41, concrete grammar carries out according to the following steps:
In mass ratio for (6��3): 1 takes IFR expanding fire retardant and metal-modified MCM-41 molecular sieve as raw material, then the raw material taken is placed in high speed disintegrator and mixes 1min, mixed raw material is placed in planetary ball mill under the rotating speed of 450r/min, grinds 30min, obtain modified IFR expanding fire retardant.
CN201610133433.3A 2016-03-09 2016-03-09 Preparation method and application of metal modified MCM-41 molecular screen Pending CN105621440A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107321303A (en) * 2017-07-28 2017-11-07 滨州学院 A kind of preparation method and applications of load Mn molecular sieves
CN112960679A (en) * 2021-04-29 2021-06-15 钛纶新材料(昆山)有限公司 Preparation method of modified MCM-41 molecular sieve

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
徐峰: "聚乙烯/介孔分子筛的制备及其热降解与燃烧行为的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107321303A (en) * 2017-07-28 2017-11-07 滨州学院 A kind of preparation method and applications of load Mn molecular sieves
CN112960679A (en) * 2021-04-29 2021-06-15 钛纶新材料(昆山)有限公司 Preparation method of modified MCM-41 molecular sieve

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