CN107952487A - A kind of preparation method of metaformaldehyde acetalation nano-porous catalyst - Google Patents
A kind of preparation method of metaformaldehyde acetalation nano-porous catalyst Download PDFInfo
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- CN107952487A CN107952487A CN201711300857.5A CN201711300857A CN107952487A CN 107952487 A CN107952487 A CN 107952487A CN 201711300857 A CN201711300857 A CN 201711300857A CN 107952487 A CN107952487 A CN 107952487A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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Abstract
The invention discloses a kind of preparation method of metaformaldehyde acetalation nano-porous catalyst, N, N dimethylformamides（DMF）, modified sodium silicate sand, aminobenzimidazole C7H7N3, imidazoles C3H4N2、Zn（NO3）2·6H2O is primary raw material, to contain the presoma of imidazoles and aminobenzimidazole as reaction ligand, with containing Zn2+Soluble-salt and modified sodium silicate sand carry out solvent thermal reaction in organic solvent, obtain amino functional ZIF types of metals organic backbone porous materials, the amino functional of invention is modified ZIF porous catalysts has higher selectivity to polymethoxy dimethyl ether, greatly save product separation costs, reactant utilization rate is improved, there is good industrial application value.
Description
Technical field
The present invention relates to a kind of metaformaldehyde acetalation nano-porous catalyst and preparation method thereof, belong to catalyst technology
Field.
Background technology
Polymethoxy dimethyl ether (polyoaymethylenedimethyletherCH30(CH2O)-CH3, DMMnOr
PODEn)
It is a kind of more ether compounds, works as DMMnMolecule Central Asia methoxyl group n<It is at normal temperatures water white transparency, volatile when 3
Liquid, has chloroform smell, can be dissolved in the water for being three times in its volume, easily dissolve each other with alcohols and ethers.Work as n>When 5, at normal temperatures
White solid.DMMnWith very high Cetane number (CN values, DMM2:63, DMM3:78, DMM4:90, DMM5:100) and contain
(oxygen content 42-49%, flash-point are 64-84 DEG C to oxygen amount, meet diesel oil safety standard, boiling point is between 156-268 DEG C, positive benefit
In in diesel range.Therefore, DMMnIt is considered as a kind of excellent environment-friendly type diesel oil blending component.In recent years, with coal chemical industry
Development, it is ripe as the technology of Material synthesis methanol using coal, the production capacity of domestic methanol in rapid growth situation, due under
It is inadequate to swim product development, causes methanol excess capacity, thus promote exploitation Downstream Products of Methanol and to high added value development for
The sound development of coal chemical industry has far reaching significance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of metaformaldehyde acetalation nano-porous catalyst, the catalysis
Agent catalytic trimerization formaldehyde acetalization can react under cryogenic, have higher activity and stability.
A kind of preparation method of metaformaldehyde acetalation nano-porous catalyst, this method comprise the following steps：
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.133g aminobenzimidazoles C7H7N3, 0.246g imidazoles C3H4N2、0.3gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；
Step 2, above-mentioned reacting coarse product is put into DMF immersions 12 it is small when, subsequent supersonic oscillations（Frequency 40Hz）, topple over upper strata
Turbid solution；
Step 3, add in above-mentioned surplus solution DMF immersions 12 it is small when, subsequent supersonic oscillations（Frequency 40Hz）, topple on
Layer turbid solution, repeats the above steps 3 times, soaking solution is changed into absolute methanol, repetitive operation 3 times, after being washed afterwards
Product；
Step 4, by the reacting coarse product after washing be put into vacuum drying chamber, vacuumized under the conditions of 50 DEG C 3 it is small when, then rise temperature
Spend to 220 DEG C keep 12 it is small when carry out high-temperature activation, then take out, that is, obtain amino functional be modified ZIF porous catalysts.
The modified sodium silicate sand preparation method is as follows：
50g water-glass sands, be added in roaster by step 1, when high-temperature roasting 2 is small at 200 DEG C, by the water-glass sand after heating
It is added to while hot in rotary grinding device, surface treating adhesive is sloughed by the grinding of 1500r/min high-speed stirreds；
Step 2, when the water-glass sand being added to sonic oscillation 3 is small in Sufficient purified water again, be washed with water to neutrality and dry, then add
Enter 15g sepiolites, 10g carbon blacks and 3g alumina laps to 500 mesh fine powders, it is uniform to add 1.8g tetrabutyl titanate mixed grindings
.
Beneficial effect：It is anti-for metaformaldehyde acetalation that ZIF porous catalysts are modified the present invention provides a kind of amino functional
Should, to contain the presoma of imidazoles and aminobenzimidazole as ligand is reacted, with containing Zn2+Soluble-salt and modified water glass
Glass sand carries out solvent thermal reaction in organic solvent, obtains amino functional ZIF types of metals organic backbone porous material crude products,
Then by amino functional ZIF types of metals organic backbone porous material crude products are washed, dry and heating, vacuum is lived
Change, obtain amino functional chemical industry types of metals organic backbone porous catalyst, surveyed by methanol and metaformaldehyde acetalation
Examination, has higher selectivity to polymethoxy dimethyl ether, greatlys save product separation costs, improves reactant utilization
Rate, has good industrial application value.
Embodiment
Embodiment 1
A kind of preparation method of metaformaldehyde acetalation nano-porous catalyst, this method comprise the following steps：
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.133g aminobenzimidazoles C7H7N3, 0.246g imidazoles C3H4N2、0.3gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；
Step 2, above-mentioned reacting coarse product is put into DMF immersions 12 it is small when, subsequent supersonic oscillations（Frequency 40Hz）, topple over upper strata
Turbid solution；
Step 3, add in above-mentioned surplus solution DMF immersions 12 it is small when, subsequent supersonic oscillations（Frequency 40Hz）, topple on
Layer turbid solution, repeats the above steps 3 times, soaking solution is changed into absolute methanol, repetitive operation 3 times, after being washed afterwards
Product；
Step 4, by the reacting coarse product after washing be put into vacuum drying chamber, vacuumized under the conditions of 50 DEG C 3 it is small when, then rise temperature
Spend to 220 DEG C keep 12 it is small when carry out high-temperature activation.Then take out, that is, obtain amino functional and be modified ZIF porous catalysts.
The modified sodium silicate sand preparation method is as follows：
50g water-glass sands, be added in roaster by step 1, when high-temperature roasting 2 is small at 200 DEG C, by the water-glass sand after heating
It is added to while hot in rotary grinding device, surface treating adhesive is sloughed by the grinding of 1500r/min high-speed stirreds；
Step 2, when the water-glass sand being added to sonic oscillation 3 is small in Sufficient purified water again, be washed with water to neutrality and dry, then add
Enter 15g sepiolites, 10g carbon blacks and 3g alumina laps to 500 mesh fine powders, it is uniform to add 1.8g tetrabutyl titanate mixed grindings
.
Embodiment 2
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.266g aminobenzimidazoles C7H7N3, 0.614g imidazoles C3H4N2、0.3gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；Remaining step is the same as embodiment 1.
Embodiment 3
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.133g aminobenzimidazoles C7H7N3, 0.246g imidazoles C3H4N2、0.8gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；Remaining step is the same as embodiment 1.
Embodiment 4
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.133g aminobenzimidazoles C7H7N3, 0.123g imidazoles C3H4N2、0.1gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；Remaining step is the same as embodiment 1.
Embodiment 5
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.368g aminobenzimidazoles C7H7N3, 0.246g imidazoles C3H4N2、0.9gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；Remaining step is the same as embodiment 1.
Embodiment 6
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.362g aminobenzimidazoles C7H7N3, 2.46g imidazoles C3H4N2、3gZn（NO3）2·6H2O, in reaction kettle
In, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover, puts
When 130 DEG C of baking oven reactions 72 are small, reacting coarse product is obtained；Remaining step is the same as embodiment 1.
Embodiment 7
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 13.3g aminobenzimidazoles C7H7N3, 1.23g imidazoles C3H4N2、1.5gZn（NO3）2·6H2O, in reaction kettle
In, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover, puts
When 130 DEG C of baking oven reactions 72 are small, reacting coarse product is obtained；Remaining step is the same as embodiment 1.
Embodiment 8
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.683g aminobenzimidazoles C7H7N3, 0.02g imidazoles C3H4N2、0.03gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；Remaining step is the same as embodiment 1.
Embodiment 9
Step 1, weigh 15gN, dinethylformamide（DMF）, 20g is modified magnesium nitrate, 20g modified sodium silicate sands are in polytetrafluoro
In ethene pyroreaction kettle, order weighs 0.133g aminobenzimidazoles C7H7N3, 0.246g imidazoles C3H4N2、0.3gZn
（NO3）2·6H2O, in reaction kettle, adds 15glDMF, uniform using magnetic stirrer, and closing lid loads stainless steel
In reaction kettle set, screw kettle cover, put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；Remaining step is the same as embodiment 1.
The modification magnesium nitrate preparation method is as follows：
The nanometer magnesium nitrate that 20g particle diameters are 30nm is put into aqueous solution, with the mixing speed machinery of 3000rpm at 20 DEG C
After stirring 15min, the aqueous dispersions of nanometer magnesium nitrate are obtained；1.5g is added into the aqueous dispersions of obtained nanometer magnesium nitrate to change
Property agent L monothio salicylic acids, at a temperature of 80 DEG C, stir under the rotating speed of 3000rpm, obtain modified Nano magnesium nitrate suspension；
The suspension of gained is spray-dried, the rotating speed of spray drying is 16000rpm, and the temperature of spray drying is 100 DEG C, is obtained
To nanometer nitric acid magnesium base composite material, average grain diameter 330nm.
Embodiment 10
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.03g aminobenzimidazoles C7H7N3, 4.246g imidazoles C3H4N2、5.3gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when, obtain reacting coarse product；Remaining step is the same as embodiment 1.
Reference examples 1
It is with 1 difference of embodiment：In the step 1 of catalyst preparation, modified sodium silicate sand is not added, remaining step and reality
It is identical to apply example 1.
Reference examples 2
It is with 1 difference of embodiment：In the step 1 of catalyst preparation, with 20g silica substituting modification water-glass sands, its
Remaining step is identical with embodiment 1.
Reference examples 3
It is with 1 difference of embodiment：In the step 1 of catalyst preparation, aminobenzimidazole is not added, remaining step and reality
It is identical to apply example 1.
Reference examples 4
It is with 1 difference of embodiment：In the step 1 of catalyst preparation, imidazoles is not added, remaining step and embodiment 1 are complete
It is exactly the same.
Reference examples 5
It is with 1 difference of embodiment：In the step 1 of catalyst preparation, Zn is not added（NO3）2·6H2O, remaining step with
Embodiment 1 is identical.
Reference examples 6
It is with 1 difference of embodiment：In the step 1 of catalyst preparation, Cu is used（NO3）2·5H2O substitutes Zn（NO3）2·6H2O,
Remaining step is identical with embodiment 1.
Reference examples 7
It is with 1 difference of embodiment：In modified sodium silicate sand preparation process 2,1.5g sepiolites, 10g carbon blacks and 3g oxygen are added
Change aluminium, remaining step is identical with embodiment 1.
Reference examples 8
It is with 1 difference of embodiment：In modified sodium silicate sand preparation process 2, with calcium oxide substitute aluminium oxide, remaining step with
Embodiment 1 is identical.
Reference examples 9
It is with 1 difference of embodiment：In modified sodium silicate sand preparation process 2, butyl titanate is not added, remaining step and reality
It is identical to apply example 1.
Reference examples 10
It is with 1 difference of embodiment：In modified sodium silicate sand preparation process 2, add 3.6g tetrabutyl titanates, remaining step with
Embodiment 1 is identical.
The catalyst that embodiment and reference examples are prepared is used for metaformaldehyde acetalation, and polymethoxy dimethyl ether exists
Carried out in the stainless steel cauldron of 110ml, reactant molar ratio CH3OH：TOX=1.2:1, loaded catalyst is the total matter of raw material
Amount 3wt%, 150 DEG C, pressure 0.5MPa of temperature, when stirring reaction 8 is small, post catalyst reaction and liquid product supercentrifuge
Separation, the product liquid obtained after centrifugation Shimadzu GC2014C type chromatographics；
It is as shown in the table for reaction result.
Test result indicates that catalyst has metaformaldehyde acetalation good catalytic effect, it is certain in reaction condition
When, polymethoxy dimethyl ether（DMM3-10）Selectivity is higher, and catalytic performance is better, otherwise poorer；In aminobenzimidazole
C7H7N3, imidazoles C3H4N2、Zn（NO3）2·6H2O mass ratioes are 1:2:When 3, other dispensings are fixed, and catalytic effect is best, with implementation
1 difference of example is that embodiment 2 to embodiment 10 changes catalyst primary raw material aminobenzimidazole C respectively7H7N3, imidazoles
C3H4N2、Zn（NO3）2·6H2The dosage and proportioning of O, has different influences to the catalytic performance of catalyst, it should be noted that real
Apply example 9 and add modified magnesium nitrate, polymethoxy dimethyl ether selectively significantly improves, and illustrates knot of the modified magnesium nitrate to catalyst
Structure activity has more preferable optimization function；Reference examples 1 are to reference examples 2 with not adding modified sodium silicate sand and taken with silica
In generation, other steps are identical, cause the activity of catalyst to change, and polymethoxy dimethyl ether selectivity is obvious to be reduced；It is right
3 aminobenzimidazole and imidazoles are not added to reference examples 6, and use Cu as usual（NO3）2·5H2O substitutes Zn（NO3）2·6H2O,
Catalytic activity reduces, and positive effect is deteriorated；Reference examples 7 to reference examples 8 change the materials proportioning of sepiolite, carbon black and aluminium oxide,
The structure of modified sodium silicate sand changes, and catalytic effect is still bad；Reference examples 9 to reference examples 10 improve tetrabutyl titanate and use
Amount, effect is still bad, illustrates that the load capacity of tetrabutyl titanate is critically important；Therefore the catalyst prepared using the present invention is to trimerization
Formaldehyde acetalization reaction has excellent catalytic effect.
Claims (2)
1. a kind of preparation method of metaformaldehyde acetalation nano-porous catalyst, it is characterised in that this method includes following step
Suddenly：
Step 1, weigh 15gN, dinethylformamide（DMF）With 20g modified sodium silicate sands in polytetrafluoroethylene (PTFE) pyroreaction kettle
In, order weighs 0.133g aminobenzimidazoles C7H7N3, 0.246g imidazoles C3H4N2、0.3gZn（NO3）2·6H2O, in reaction
In kettle, 15glDMF is added, uniform using magnetic stirrer, closing lid loads in stainless steel cauldron set, screws kettle cover,
Put 130 DEG C of baking ovens reaction 72 it is small when or so, obtain reacting coarse product；
Step 2, above-mentioned reacting coarse product is put into DMF immersions 12 it is small when, subsequent supersonic oscillations, topple over upper strata turbid solution；
Step 3, add in above-mentioned surplus solution DMF immersions 12 it is small when, subsequent supersonic oscillations, topple over upper strata turbid solution,
Repeat the above steps 3 times, soaking solution is changed into absolute methanol, repetitive operation 3 times, the product after being washed afterwards；
Step 4, by the reacting coarse product after washing be put into vacuum drying chamber, vacuumized under the conditions of 50 DEG C 3 it is small when, then rise temperature
Spend to 220 DEG C keep 12 it is small when carry out high-temperature activation, then take out, that is, obtain amino functional be modified ZIF porous catalysts.
A kind of 2. preparation method of metaformaldehyde acetalation nano-porous catalyst according to claim 1, it is characterised in that
The modified sodium silicate sand preparation method is as follows：
50g water-glass sands, be added in roaster by step 1, when high-temperature roasting 2 is small at 200 DEG C, by the water-glass sand after heating
It is added to while hot in rotary grinding device, surface treating adhesive is sloughed by the grinding of 1500r/min high-speed stirreds；
Step 2, when the water-glass sand being added to sonic oscillation 3 is small in Sufficient purified water again, be washed with water to neutrality and dry, then add
Enter 15g sepiolites, 10g carbon blacks and 3g alumina laps to 500 mesh fine powders, it is uniform to add 1.8g tetrabutyl titanate mixed grindings
.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307482A (en) * | 2014-10-14 | 2015-01-28 | 中国科学院宁波材料技术与工程研究所 | Functionalized ZIF type metal organic framework (MOF) porous material as well as preparation method and application of material |
| CN104312375A (en) * | 2014-09-15 | 2015-01-28 | 天长市巨龙车船涂料有限公司 | Wear-resistant scratch-resistant anti-ultraviolet paint for ships and preparation method thereof |
| CN106495996A (en) * | 2016-10-21 | 2017-03-15 | 中国石油大学(北京) | A kind of method with lewis acid as catalyst preparation polymethoxy dimethyl ether |
| CN107384048A (en) * | 2017-08-29 | 2017-11-24 | 王迅 | A kind of preparation method of oceanographic equipment nano-antirust coating |
-
2017
- 2017-12-10 CN CN201711300857.5A patent/CN107952487A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312375A (en) * | 2014-09-15 | 2015-01-28 | 天长市巨龙车船涂料有限公司 | Wear-resistant scratch-resistant anti-ultraviolet paint for ships and preparation method thereof |
| CN104307482A (en) * | 2014-10-14 | 2015-01-28 | 中国科学院宁波材料技术与工程研究所 | Functionalized ZIF type metal organic framework (MOF) porous material as well as preparation method and application of material |
| CN106495996A (en) * | 2016-10-21 | 2017-03-15 | 中国石油大学(北京) | A kind of method with lewis acid as catalyst preparation polymethoxy dimethyl ether |
| CN107384048A (en) * | 2017-08-29 | 2017-11-24 | 王迅 | A kind of preparation method of oceanographic equipment nano-antirust coating |
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Application publication date: 20180424 |