CN114349779B - Modified silicon dioxide particle chlorine removing agent and preparation method and application thereof - Google Patents
Modified silicon dioxide particle chlorine removing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN114349779B CN114349779B CN202111637250.2A CN202111637250A CN114349779B CN 114349779 B CN114349779 B CN 114349779B CN 202111637250 A CN202111637250 A CN 202111637250A CN 114349779 B CN114349779 B CN 114349779B
- Authority
- CN
- China
- Prior art keywords
- reaction
- contact reaction
- modified silica
- organic solvent
- chlorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000460 chlorine Substances 0.000 title claims abstract description 83
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 82
- 239000002245 particle Substances 0.000 title claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 32
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 24
- YFIBSNDOVCWPBL-UHFFFAOYSA-N hexa-1,5-diyne Chemical compound C#CCCC#C YFIBSNDOVCWPBL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 17
- 235000010378 sodium ascorbate Nutrition 0.000 claims abstract description 15
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims abstract description 15
- 229960005055 sodium ascorbate Drugs 0.000 claims abstract description 15
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 21
- -1 -tert-butyl furancarboxylate Chemical compound 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002516 radical scavenger Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229960003529 diazepam Drugs 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- RYKYAZRLLWSNJG-UHFFFAOYSA-K C(C)(C)(C)C1=CC=C(O1)C(=O)[O-].[Cr+3].C(C)(C)(C)C1=CC=C(O1)C(=O)[O-].C(C)(C)(C)C1=CC=C(O1)C(=O)[O-] Chemical compound C(C)(C)(C)C1=CC=C(O1)C(=O)[O-].[Cr+3].C(C)(C)(C)C1=CC=C(O1)C(=O)[O-].C(C)(C)(C)C1=CC=C(O1)C(=O)[O-] RYKYAZRLLWSNJG-UHFFFAOYSA-K 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- DPJLYHSRYDWGOD-UHFFFAOYSA-N [Si](=O)=O.[Cl] Chemical class [Si](=O)=O.[Cl] DPJLYHSRYDWGOD-UHFFFAOYSA-N 0.000 description 9
- 239000003377 acid catalyst Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Compounds (AREA)
Abstract
The application provides a modified silicon dioxide particle chlorine removing agent and a preparation method and application thereof, firstly, in a first organic solvent, in the presence of copper sulfate pentahydrate and sodium ascorbate as catalysts and in the atmosphere of protective gas, dripping a mixed solution of 1, 5-hexadiyne and 3, 5-diazinobenzoic acid into the first organic solvent for a first contact reaction to obtain a first product; further, extracting and separating the first product to obtain an organic phase of the first product, drying the organic phase, filtering and performing rotary evaporation to obtain an intermediate I; further, in a second organic solvent, under the action of a chromium 5-tert-butylfurancarboxylate serving as a catalyst, carrying out a second contact reaction on the mixed solution of the intermediate I and KH560, carrying out rotary evaporation to obtain an intermediate II, soaking silica particles in a weak acid aqueous solution, controlling the addition of the intermediate II to carry out a third contact reaction, and filtering out the silica particles after the reaction is finished to obtain the modified silica particle chlorine remover.
Description
Technical Field
The application relates to the technical field of chlorine removal agents, in particular to a modified silicon dioxide particle chlorine removal agent, a preparation method and application thereof.
Background
With the continuous development of the electronic industry and the continuous innovation of products such as electronic chips, epoxy resins are used as adhesives commonly used in the electronic industry, and have raised higher requirements in terms of quality.
An intermediate epichlorohydrin is generated during the preparation of the epoxy resin, and thus the finally prepared epoxy resin is inevitably doped with chlorine. If the chlorine content in the epoxy resin is too high, the soluble chlorine in the epoxy resin is hydrolyzed in a high temperature and high pressure environment to generate hydrochloric acid during the semiconductor packaging and bonding process, thereby corroding the electronic device, and thus the epoxy resin applied to the electronic industry is required to have a relatively low chlorine content.
In the related art, chlorine elements generated in the preparation process of epoxy resin are generally removed in two ways, the first is to reduce organic chlorine generated by side reaction aiming at the synthesis process of epoxy resin, then the organic chlorine is hydrolyzed into inorganic chlorine by utilizing a phase transfer catalyst, and finally hydrogen chloride is removed by a strong alkali solution. The second is to further remove chlorine by using chlorine removing agent for the synthesized epoxy resin, but the chlorine removing agent has high cost and is disposable at present, and the chlorine removing agent needs to be replaced after one time use. Therefore, how to realize the recycling of the chlorine removal agent on the basis of higher chlorine removal effect is a technical problem to be solved urgently by the technicians in the field.
Disclosure of Invention
The application provides a modified silicon dioxide particle chlorine removing agent, a preparation method and application thereof, wherein the chlorine removing agent has a unique annular structure, hydrogen ions can be captured through polar C-H bonds, and meanwhile, the chlorine removing agent can be recycled, so that the problems of insignificant chlorine removing effect and high cost in the traditional technical center are solved.
The technical scheme adopted by the application for solving the technical problems is as follows:
in a first aspect, the present application provides a method for preparing a modified silica particle chlorine scavenger comprising the steps of:
in a first organic solvent, dropwise adding a mixed solution of 1, 5-hexadiyne and 3, 5-diazinobenzoic acid into the first organic solvent in the presence of copper sulfate pentahydrate, sodium ascorbate and protective gas to perform a first contact reaction to obtain a first product;
extracting and separating the first product to obtain an organic phase of the first product;
drying the organic phase, filtering and then performing rotary evaporation to obtain an intermediate I;
in a second organic solvent, under the action of a catalyst which is chromium 5-tert-butyl furancarboxylate, carrying out a second contact reaction on the mixed solution of the intermediate I and KH560, and carrying out rotary evaporation to obtain an intermediate II;
soaking silica particles in weak acid aqueous solution, adding the intermediate II under control to perform a third contact reaction, and filtering out the silica particles after the reaction is finished to obtain a modified silica particle chlorine removing agent;
wherein the first contact reaction, the second contact reaction and the third contact reaction are all carried out in a reactor.
Optionally, the first organic solvent comprises a mixed liquid of water and tertiary butanol, and the protective gas is argon;
the conditions of the first contact reaction include: and slowly dropwise adding the mixed solution of the 1, 5-hexadiyne and the 3, 5-diazepine benzoic acid when the temperature is raised to 60-65 ℃, wherein the dropwise adding time is controlled to be 4-5h, and the reaction time is controlled to be 12-14h.
Optionally, the method further comprises:
after the first contact reaction is completed, cooling the first product to room temperature;
extracting and separating the first product by using dichloromethane to obtain the first product;
the organic phase was dried over anhydrous sodium sulfate, filtered and the dichloromethane was removed by rotary evaporation to give intermediate i.
Optionally, the second organic solvent comprises toluene;
the conditions of the second contact reaction include: the reaction is carried out for 5 to 6 hours at the reaction temperature of 120 to 140 ℃.
Optionally, the conditions of the third contact reaction include: the reaction is stirred for 1 to 2 hours at the temperature of 30 to 40 ℃.
Optionally, the mass ratio of water to tertiary butanol in the first organic solvent is 1:1, the addition amount is 70-80wt% of the total mass;
the molar ratio of the 1, 5-hexadiyne to the 3, 5-diazepam benzoic acid is (1-1.2): 1, a step of;
the molar ratio of the copper sulfate pentahydrate to the sodium ascorbate is 1: the addition amount of 2 is 40-50wt% of the total mass of 1, 5-hexadiyne and 3, 5-diazepinic acid.
Alternatively, the molar ratio of intermediate i to KH560 is 1: (2-2.2), wherein the addition amount of the 5-tert-butyl chromium furancarboxylate is 3-5wt% of the total mass of the intermediate I and KH 560;
the addition amount of toluene in the second organic solvent is 70-80wt%.
Optionally, the mass of the silica particles and the intermediate II is 1:1, the pH of the weak acid aqueous solution is 5-6, and the addition amount is 60-70wt%.
In a second aspect, the application provides a modified silica particle chlorine scavenger having the following structural formula:
in a third aspect, the present application provides the use of a modified silica particle chlorine scavenger, such as the use of a modified silica particle chlorine scavenger as described above in the synthesis of an epoxy resin.
The technical scheme provided by the application has the following beneficial technical effects:
the application provides a modified silicon dioxide particle chlorine removing agent and a preparation method and application thereof, wherein the preparation method comprises the steps of firstly, dropwise adding a mixed solution of 1, 5-hexadiyne and 3, 5-diazide benzoic acid into a first organic solvent in the presence of copper sulfate pentahydrate and sodium ascorbate serving as catalysts and protective gas to perform a first contact reaction to obtain a first product; further, extracting and separating the first product to obtain an organic phase of the first product, drying the organic phase, filtering and performing rotary evaporation to obtain an intermediate I; further, in a second organic solvent, under the action of a chromium 5-tert-butylfurancarboxylate catalyst, carrying out a second contact reaction on the mixed solution of the intermediate I and KH560, carrying out rotary evaporation to obtain an intermediate II, soaking silica particles in a weak acid aqueous solution, controlling the addition of the intermediate II to carry out a third contact reaction, and filtering out the silica particles after the reaction is finished to obtain the modified silica particle chlorine remover. The preparation method of the modified silicon dioxide particle chlorine removal agent provided by the embodiment of the application is simple, the reaction mechanism is clear, and the modified silicon dioxide particle chlorine removal agent can be recycled. The modified silicon dioxide particle chlorine remover prepared by the method utilizes the unique annular structure to capture chloride ions in the epoxy resin, can further reduce the chlorine content in the epoxy resin, reduces the generation of hydrochloric acid by hydrolysis of hydrolyzable chlorine in the epoxy resin under high temperature and high pressure, thereby reducing the risk of corrosion to components and circuit boards, and simultaneously utilizes KH560 to graft on the silicon dioxide particles, so that the chlorine remover is insoluble in water, and can remove the chloride ions captured by the chlorine remover through flushing, thereby realizing the recycling of the chlorine remover.
Drawings
In order to more clearly illustrate the technical solution of the present application, the drawings that are needed in the embodiments will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a diagram showing the synthesis and chlorine removal mechanism of a modified silica chlorine removal agent according to an embodiment of the present application.
Detailed Description
In order to enable those skilled in the art to better understand the technical solutions of the present application, the technical solutions of the application embodiments will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application; it will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, shall fall within the scope of the present application.
The first aspect of the embodiment of the application provides a modified silicon dioxide particle chlorine removing agent, which has the following structural formula:
the capture mechanism of the modified silicon dioxide particle chlorine removing agent provided by the embodiment of the application on chloride ions is shown as follows:
as can be seen from the above formula, the prepared modified silicon dioxide chlorine removing agent has a cyclic structure, 6 polarized C-H bonds exist on the 1,2, 3-triazole ring and the benzene ring, the capture of Cl < - > can be realized, and the structure is stable. Meanwhile, based on the unique annular structure of the chlorine removing agent, hydrogen ions can be captured through polar C-H bonds, and meanwhile, the chlorine removing agent can be recycled.
The second aspect of the present application provides a method for preparing a modified silica chlorine scavenger, and prepared by:
when the modified silicon dioxide chlorine removing agent is prepared, firstly, 1, 5-hexadiyne and 3, 5-diazinobenzoic acid are used as raw materials, cupric sulfate pentahydrate and sodium ascorbate are used as catalysts, an intermediate I is obtained through click reaction of azide and alkyne, secondly, KH560 and the intermediate I are used for carrying out esterification reaction in the presence of an acid catalyst to obtain an intermediate II, and finally methoxy groups of the intermediate II and hydroxyl groups on silicon dioxide particles are used for removing methanol, so that the intermediate II is grafted on the silicon dioxide particles.
Referring to fig. 1, fig. 1 is a diagram of synthesis and chlorine removal mechanism of a modified silica chlorine removal agent according to an embodiment of the present application, and as shown in fig. 1, a preparation method of the modified silica chlorine removal agent includes the following steps:
1) Adding mixed liquid of water and tertiary butanol into a three-neck flask as a solvent, adding copper sulfate pentahydrate and sodium ascorbate as catalysts, heating to 60-65 ℃, then dissolving a certain amount of 1, 5-hexadiyne and 3, 5-diazepinic acid into a mixed solvent of a small amount of water and tertiary butanol, slowly dropwise adding the mixed solvent into the three-neck flask, keeping the dropwise adding time at 4-5h, and reacting for 12-14h. And argon is protected in the whole process. After the reaction, cooling to room temperature, extracting with dichloromethane, separating to obtain an organic phase, drying with anhydrous sodium sulfate, filtering, and removing dichloromethane by rotary evaporation to obtain an intermediate I. Wherein the mass ratio of water to tertiary butanol in the mixed solvent is 1:1, the addition amount is 70-80wt% of the total mass; the molar ratio of 1, 5-hexadiyne to 3, 5-diazepinic acid is (1-1.2): 1, a step of; the molar ratio of the copper sulfate pentahydrate to the sodium ascorbate is 1:2. the addition amount is 40-50wt% of the total mass of the 1, 5-hexadiyne and the 3, 5-diazepam benzoic acid.
2) Dissolving the intermediate I and KH560 in toluene, adding chromium 5-tert-butyl furancarboxylate as acid catalyst, reacting at 120-140 deg.C for 5-6 hr, and removing toluene by rotary evaporation to obtain intermediate II. Wherein the molar ratio of the intermediate I to KH560 is 1: (2-2.2); the addition amount of the 5-tert-butyl chromium furancarboxylate is 3-5wt% of the total mass of the intermediate I and KH 560; the addition amount of toluene is 70-80wt%.
3) Soaking silica particles in weak acid water solution, adding the intermediate II, stirring at 30-40 ℃ for reaction for 1-2h, and filtering out the silica particles to obtain the modified silica particle chlorine removing agent. Wherein the mass of the silica particles and the intermediate II is 1:1, the pH of the weak acid solution is 5-6, and the addition amount is 60-70wt%.
The method is further described with reference to specific examples and figures:
example 1
Into a three-necked flask equipped with a stirrer, 72.12g of a mixed solvent (mass ratio of water to t-butanol: 1:1) was charged, followed by 11.28g of a catalyst (molar ratio of copper sulfate pentahydrate to sodium ascorbate: 1:2) and the temperature was raised to 60 ℃. Then 7.8g (0.1 mol) of 1, 5-hexadiyne and 20.4g (0.1 mol) of 3, 5-diazepinic acid are dissolved in 20g of mixed solvent and slowly added into a three-neck flask in a dropwise manner, the dropwise addition time is kept for 4 hours, the reaction is carried out for 12 hours, and the whole argon protection is realized. After the reaction, the obtained product was cooled to room temperature, extracted with dichloromethane, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered and the dichloromethane was removed by rotary evaporation to obtain intermediate i.
28.2g (0.05 mol) of intermediate I and 23.4g (0.1 mol) of KH560 were dissolved in 123.67g of toluene, 1.55g of chromium 5-t-butylfurancarboxylate was added as an acid catalyst, and the mixture was reacted at 120℃for 5 hours, after the completion of the reaction, toluene was removed by rotary evaporation to obtain intermediate II.
10g of silicon dioxide particles are soaked in 30g of weak acid aqueous solution with pH value of 5, then 10g of intermediate II is added, stirring reaction is carried out for 1h at 30 ℃, and the silicon dioxide particles are filtered out, thus obtaining the modified silicon dioxide particle chlorine removing agent.
Example 2
158.56g of the mixed solvent (water to t-butanol mass ratio: 1:1) was charged into a three-necked flask equipped with a stirrer, followed by 14.88g of the catalyst (in which the molar ratio of copper sulfate pentahydrate to sodium ascorbate was 1:2) and the temperature was raised to 65 ℃. Then 9.36g (0.12 mol) of 1, 5-hexadiyne and 20.4g (0.1 mol) of 3, 5-diazepinic acid are dissolved in 20g of mixed solvent and slowly added into a three-neck flask in a dropwise manner, the dropwise addition time is kept at 5h, the reaction is carried out for 14h, and the whole argon protection is realized. After the reaction, the obtained product was cooled to room temperature, extracted with dichloromethane, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered and the dichloromethane was removed by rotary evaporation to obtain intermediate i.
28.2g (0.05 mol) of intermediate I and 25.74g (0.11 mol) of KH560 were dissolved in 226.56g of toluene, 2.7g of chromium 5-t-butylfurancarboxylate was added as an acid catalyst, and the mixture was reacted at 140℃for 6 hours, after the completion of the reaction, toluene was removed by rotary evaporation to obtain intermediate II.
10g of silicon dioxide particles are soaked in 46.7g of weak acid aqueous solution with pH of 6, then 10g of intermediate II is added, stirring reaction is carried out for 1h at 30 ℃, and the silicon dioxide particles are filtered out, thus obtaining the modified silicon dioxide particle chlorine removing agent.
Example 3
78.96g of the mixed solvent (water to t-butanol mass ratio: 1:1) was charged into a three-necked flask equipped with a stirrer, followed by 12.36g of the catalyst (in which the molar ratio of copper sulfate pentahydrate to sodium ascorbate was 1:2) and the temperature was raised to 65 ℃. Then 7.8g (0.1 mol) of 1, 5-hexadiyne and 20.4g (0.1 mol) of 3, 5-diazepinic acid are dissolved in 20g of mixed solvent and slowly added into a three-neck flask in a dropwise manner, the dropwise addition time is kept at 5h, the reaction is carried out for 12h, and the whole argon protection is realized. After the reaction, the obtained product was cooled to room temperature, extracted with dichloromethane, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered and the dichloromethane was removed by rotary evaporation to obtain intermediate i.
28.2g (0.05 mol) of intermediate I and 23.4g (0.1 mol) of KH560 were dissolved in 140g of toluene, 1.63g of chromium 5-t-butylfurancarboxylate was added as an acid catalyst, and the mixture was reacted at 130℃for 5 hours, after the completion of the reaction, toluene was removed by rotary evaporation to obtain intermediate II.
10g of silicon dioxide particles are soaked in 30g of weak acid aqueous solution with pH of 6, then 10g of intermediate II is added, stirring reaction is carried out for 1h at 40 ℃, and the silicon dioxide particles are filtered out, thus obtaining the modified silicon dioxide particle chlorine removing agent.
Example 4
Into a three-necked flask equipped with a stirrer, 72.12g of a mixed solvent (mass ratio of water to t-butanol: 1:1) was charged, followed by 11.69g of a catalyst (molar ratio of copper sulfate pentahydrate to sodium ascorbate: 1:2) and the temperature was raised to 60 ℃. Then 7.8g (0.1 mol) of 1, 5-hexadiyne and 20.4g (0.1 mol) of 3, 5-diazepinic acid are dissolved in 20g of mixed solvent and slowly added into a three-neck flask in a dropwise manner, the dropwise addition time is kept at 5h, the reaction is carried out for 12h, and the whole argon protection is realized. After the reaction, the obtained product was cooled to room temperature, extracted with dichloromethane, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered and the dichloromethane was removed by rotary evaporation to obtain intermediate i.
28.2g (0.05 mol) of intermediate I and 23.4g (0.1 mol) of KH560 were dissolved in 143.8g of toluene, 1.82g of chromium 5-t-butylfurancarboxylate was added as an acid catalyst, and the mixture was reacted at 140℃for 6 hours, after the completion of the reaction, toluene was removed by rotary evaporation to obtain intermediate II.
10g of silicon dioxide particles are soaked in 46.7g of weak acid aqueous solution with pH of 5, then 10g of intermediate II is added, stirring reaction is carried out for 2 hours at 30 ℃, and the silicon dioxide particles are filtered out, thus obtaining the modified silicon dioxide particle chlorine removing agent.
Example 5
146.32g of the mixed solvent (water to t-butanol mass ratio: 1:1) was charged into a three-necked flask equipped with a stirrer, followed by 14.63g of the catalyst (in which the molar ratio of copper sulfate pentahydrate to sodium ascorbate was 1:2) and the temperature was raised to 60 ℃. Then 9.36g (0.12 mol) of 1, 5-hexadiyne and 20.4g (0.1 mol) of 3, 5-diazepinic acid are dissolved in 20g of mixed solvent and slowly added into a three-neck flask in a dropwise manner, the dropwise addition time is kept at 5h, the reaction is carried out for 13h, and the whole argon protection is realized. After the reaction, the obtained product was cooled to room temperature, extracted with dichloromethane, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered and the dichloromethane was removed by rotary evaporation to obtain intermediate i.
28.2g (0.05 mol) of intermediate I and 25.74g (0.11 mol) of KH560 were dissolved in 216.74g of toluene, 2.51g of chromium 5-t-butylfurancarboxylate was added as an acid catalyst, and the mixture was reacted at 140℃for 5 hours, after the completion of the reaction, toluene was removed by rotary evaporation to obtain intermediate II.
10g of silicon dioxide particles are soaked in 35g of weak acid aqueous solution with pH of 6, then 10g of intermediate II is added, stirring reaction is carried out for 2 hours at 40 ℃, and the silicon dioxide particles are filtered out, thus obtaining the modified silicon dioxide particle chlorine removing agent.
Example 6
136.3g of the mixed solvent (water to t-butanol mass ratio: 1:1) was charged into a three-necked flask equipped with a stirrer, followed by 14.23g of the catalyst (in which the molar ratio of copper sulfate pentahydrate to sodium ascorbate was 1:2) and the temperature was raised to 65 ℃. Then 9.36g (0.12 mol) of 1, 5-hexadiyne and 20.4g (0.1 mol) of 3, 5-diazepinic acid are dissolved in 20g of mixed solvent and slowly added into a three-neck flask in a dropwise manner, the dropwise addition time is kept at 5h, the reaction is carried out for 12h, and the whole argon protection is realized. After the reaction, the obtained product was cooled to room temperature, extracted with dichloromethane, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered and the dichloromethane was removed by rotary evaporation to obtain intermediate i.
28.2g (0.05 mol) of intermediate I and 25.74g (0.11 mol) of KH560 were dissolved in 170.68g of toluene, 2.43g of chromium 5-t-butylfurancarboxylate was added as an acid catalyst, and the mixture was reacted at 120℃for 6 hours, after the completion of the reaction, toluene was removed by rotary evaporation to obtain intermediate II.
10g of silicon dioxide particles are soaked in 40g of weak acid aqueous solution with pH of 6, then 10g of intermediate II is added, stirring reaction is carried out for 1h at 30 ℃, and the silicon dioxide particles are filtered out, thus obtaining the modified silicon dioxide particle chlorine removing agent.
In order to characterize the chlorine removal efficiency of a modified silica chlorine scavenger, the total chlorine content was first determined using the oxygen bottle method for an epoxy resin prepared by conventional chlorine removal, and then the epoxy resin was treated with the modified silica chlorine scavenger of the present application, and then the total chlorine content was determined again, and the experimental results are shown in table 1.
TABLE 1
As can be seen from the table, the total chlorine content of the epoxy resin treated by the modified silicon dioxide chlorine scavenger is obviously reduced, the value of the epoxy resin can meet the industrial requirements of electronic components, and the risk that the hydrolyzable chlorine in the epoxy resin is hydrolyzed to generate hydrochloric acid under high temperature and high pressure so as to corrode components and circuit boards can be further reduced
In order to characterize the recycling property of the modified silicon dioxide chlorine removal agent, the modified silicon dioxide chlorine removal agent obtained after the experiment is filtered and filtered, and after the modified silicon dioxide chlorine removal agent is cleaned for a plurality of times by deionized water, the epoxy resin before and after the treatment is tested by the oxygen bottle method again, and the experimental results are shown in table 2.
TABLE 2
The results in the table show that the chlorine removal agent obtained after washing by the deionized water still has corresponding chlorine removal effect when being reused, which indicates that the recyclable chlorine removal agent can be reused for a plurality of times, and the cost is saved.
As a further improvement of the embodiment of the application, the modified silicon dioxide chlorine removing agent is used in the following way that after the epoxy resin is synthesized, the modified silicon dioxide chlorine removing agent and the prepared epoxy resin are mixed according to the mass ratio of 1:1 are mixed and added into a hydrophobic organic solvent, and are heated for 3 to 4 hours at the temperature of 80 to 90 ℃. After the reaction is finished, the modified silicon dioxide chlorine removing agent is filtered and can be recycled after being washed by deionized water for a plurality of times.
In summary, the modified silicon dioxide particle chlorine removal agent provided by the embodiment of the application, as well as the preparation method and application thereof, has the advantages of simple preparation method, clear reaction mechanism and capability of recycling. The unique ring structure is utilized to capture chloride ions in the epoxy resin, so that the chlorine content in the epoxy resin can be further reduced, the hydrolyzable chlorine in the epoxy resin can be hydrolyzed to generate hydrochloric acid under high temperature and high pressure, the risk of corrosion to components and circuit boards is reduced, KH560 is utilized to graft on silicon dioxide particles, the chlorine scavenger is insoluble in water, and the chloride ions captured by the chlorine scavenger can be removed through flushing, so that the recycling of the chlorine scavenger is realized.
It is noted that relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
It will be understood that the application is not limited to what has been described above and shown in the drawings, and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.
Claims (9)
1. The application of the modified silicon dioxide particle chlorine remover is characterized by comprising the following structural formula:
the application of the modified silica particle chlorine remover in the synthesis of epoxy resin.
2. The use of a modified silica particle chlorine scavenger according to claim 1, wherein the modified silica particle chlorine scavenger is prepared by a process comprising the steps of:
in a first organic solvent, dropwise adding a mixed solution of 1, 5-hexadiyne and 3, 5-diazinobenzoic acid into the first organic solvent in the presence of copper sulfate pentahydrate, sodium ascorbate and protective gas to perform a first contact reaction to obtain a first product;
extracting and separating the first product to obtain an organic phase of the first product;
drying the organic phase, filtering and then performing rotary evaporation to obtain an intermediate I;
in a second organic solvent, under the action of a catalyst which is chromium 5-tert-butyl furancarboxylate, carrying out a second contact reaction on the mixed solution of the intermediate I and KH560, and carrying out rotary evaporation to obtain an intermediate II;
soaking silica particles in weak acid aqueous solution, adding the intermediate II under control to perform a third contact reaction, and filtering out the silica particles after the reaction is finished to obtain a modified silica particle chlorine removing agent;
wherein the first contact reaction, the second contact reaction and the third contact reaction are all carried out in a reactor.
3. The use of a modified silica particle chlorine scavenger according to claim 2 wherein the first organic solvent comprises a mixed liquid of water and t-butanol and the shielding gas is argon;
the conditions of the first contact reaction include: and slowly dropwise adding the mixed solution of the 1, 5-hexadiyne and the 3, 5-diazepine benzoic acid when the temperature is raised to 60-65 ℃, wherein the dropwise adding time is controlled to be 4-5h, and the reaction time is controlled to be 12-14h.
4. The use of a modified silica particle chlorine scavenger according to claim 2, wherein the method further comprises:
after the first contact reaction is completed, cooling the first product to room temperature;
extracting and separating the first product by using dichloromethane to obtain the first product;
the organic phase was dried over anhydrous sodium sulfate, filtered and the dichloromethane was removed by rotary evaporation to give intermediate i.
5. The use of a modified silica particle chlorine scavenger according to claim 2 wherein the second organic solvent comprises toluene;
the conditions of the second contact reaction include: the reaction is carried out for 5 to 6 hours at the reaction temperature of 120 to 140 ℃.
6. The use of a modified silica particle chlorine scavenger according to claim 2 wherein the conditions of the third contact reaction comprise: the reaction is stirred for 1 to 2 hours at the temperature of 30 to 40 ℃.
7. Use of modified silica particles according to claim 3, wherein the mass ratio of water to t-butanol in the first organic solvent is 1:1, the addition amount is 70-80wt% of the total mass;
the molar ratio of the 1, 5-hexadiyne to the 3, 5-diazepam benzoic acid is (1-1.2): 1, a step of;
the molar ratio of the copper sulfate pentahydrate to the sodium ascorbate is 1: the addition amount of 2 is 40-50wt% of the total mass of 1, 5-hexadiyne and 3, 5-diazepinic acid.
8. The use of modified silica particles as claimed in claim 5, wherein the molar ratio of intermediate i to KH560 is 1: (2-2.2), wherein the addition amount of the 5-tert-butyl chromium furancarboxylate is 3-5wt% of the total mass of the intermediate I and KH 560;
the addition amount of toluene in the second organic solvent is 70-80wt%.
9. Use of modified silica particles as claimed in claim 2, wherein the mass of silica particles and intermediate ii is 1:1, the pH of the weak acid aqueous solution is 5-6, and the addition amount is 60-70wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111637250.2A CN114349779B (en) | 2021-12-29 | 2021-12-29 | Modified silicon dioxide particle chlorine removing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111637250.2A CN114349779B (en) | 2021-12-29 | 2021-12-29 | Modified silicon dioxide particle chlorine removing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114349779A CN114349779A (en) | 2022-04-15 |
| CN114349779B true CN114349779B (en) | 2023-09-26 |
Family
ID=81104334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111637250.2A Active CN114349779B (en) | 2021-12-29 | 2021-12-29 | Modified silicon dioxide particle chlorine removing agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114349779B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3822235A (en) * | 1971-04-30 | 1974-07-02 | Philips Corp | Method of producing light-sensitive epoxy resins |
| CN1379765A (en) * | 1999-10-15 | 2002-11-13 | 弗·哈夫曼-拉罗切有限公司 | Benzodiazepine derivatives usable as parental metabolic glutamate receptor antagonist |
| CN101948405A (en) * | 2010-09-09 | 2011-01-19 | 同济大学 | Method for preparing bromoaryl azide |
| CN102675484A (en) * | 2012-05-18 | 2012-09-19 | 华南理工大学 | Synthetic method of 4-hydrazoic benzoyl chitosan |
| KR20160017522A (en) * | 2014-08-06 | 2016-02-16 | 경희대학교 산학협력단 | Zirconium-based implants with modified surface , zirconium-based implants for inducing or promoting osteogenesis and manufacturing method of the sames |
| KR101806495B1 (en) * | 2017-07-10 | 2017-12-08 | (주) 비제이파워 | Polymer toughened epoxy resin composition |
| CN108440409A (en) * | 2018-03-16 | 2018-08-24 | 济南爱思医药科技有限公司 | A kind of green high-efficient preparation method of Rebamipide |
| CN109096507A (en) * | 2018-07-09 | 2018-12-28 | 浙江工业大学 | A kind of material and the preparation method and application thereof of the triphen amine derivant based on imidazole type ion liquid modification |
| CN110201643A (en) * | 2019-06-13 | 2019-09-06 | 魏健 | A kind of antichlor of high-efficient and lasting and preparation method thereof |
| CN111333741A (en) * | 2020-03-03 | 2020-06-26 | 广东省石油与精细化工研究院 | High molecular compound dechlorinating agent and preparation method thereof |
| CN112592488A (en) * | 2020-12-15 | 2021-04-02 | 桐乡市璟维信息科技有限公司 | Preparation method and application of carbon nanotube modified polystyrene conductive material |
-
2021
- 2021-12-29 CN CN202111637250.2A patent/CN114349779B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3822235A (en) * | 1971-04-30 | 1974-07-02 | Philips Corp | Method of producing light-sensitive epoxy resins |
| CN1379765A (en) * | 1999-10-15 | 2002-11-13 | 弗·哈夫曼-拉罗切有限公司 | Benzodiazepine derivatives usable as parental metabolic glutamate receptor antagonist |
| CN101948405A (en) * | 2010-09-09 | 2011-01-19 | 同济大学 | Method for preparing bromoaryl azide |
| CN102675484A (en) * | 2012-05-18 | 2012-09-19 | 华南理工大学 | Synthetic method of 4-hydrazoic benzoyl chitosan |
| KR20160017522A (en) * | 2014-08-06 | 2016-02-16 | 경희대학교 산학협력단 | Zirconium-based implants with modified surface , zirconium-based implants for inducing or promoting osteogenesis and manufacturing method of the sames |
| KR101806495B1 (en) * | 2017-07-10 | 2017-12-08 | (주) 비제이파워 | Polymer toughened epoxy resin composition |
| CN108440409A (en) * | 2018-03-16 | 2018-08-24 | 济南爱思医药科技有限公司 | A kind of green high-efficient preparation method of Rebamipide |
| CN109096507A (en) * | 2018-07-09 | 2018-12-28 | 浙江工业大学 | A kind of material and the preparation method and application thereof of the triphen amine derivant based on imidazole type ion liquid modification |
| CN110201643A (en) * | 2019-06-13 | 2019-09-06 | 魏健 | A kind of antichlor of high-efficient and lasting and preparation method thereof |
| CN111333741A (en) * | 2020-03-03 | 2020-06-26 | 广东省石油与精细化工研究院 | High molecular compound dechlorinating agent and preparation method thereof |
| CN112592488A (en) * | 2020-12-15 | 2021-04-02 | 桐乡市璟维信息科技有限公司 | Preparation method and application of carbon nanotube modified polystyrene conductive material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114349779A (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108299343B (en) | Method for preparing 3, 4-epoxy cyclohexyl methyl (meth) acrylate by using microchannel reactor | |
| CN105754071A (en) | Preparation technology of bisphenol fluorene epoxy resin | |
| CN101219935B (en) | Bromol production method | |
| CN114349779B (en) | Modified silicon dioxide particle chlorine removing agent and preparation method and application thereof | |
| CN114349887B (en) | Epoxy resin chlorine removing agent and preparation method and application thereof | |
| JPH01125341A (en) | 2, 5-bis (2, 2, 2-trifluoroethoxy)acetophenone and its production | |
| CN111620769B (en) | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride | |
| JPH11255753A (en) | Triallyl isocyanurate having high quality level, and its production | |
| CN108484531A (en) | A kind of synthesis technology of terephthalic acid diglycidyl ester | |
| CN112028748B (en) | Preparation method of 2, 5-dimethoxychlorobenzene | |
| CN114395061B (en) | Chlorine removing agent and preparation method and application thereof | |
| CN101492381B (en) | Method of preparing 2,2-di(3-amino-4-hydroxyl phenyl) hexafluoroacetore | |
| CN114195981A (en) | Biphenyl epoxy resin and synthetic method and application thereof | |
| CN114210365B (en) | Catalyst for synthesizing methyl ethyl carbonate and diethyl carbonate and method thereof | |
| CN109503358A (en) | A kind of preparation method of isooctyl acid copper | |
| CN111253272B (en) | Method for preparing benzamide compound | |
| CN111217718B (en) | Sulfur-free 2-bromo-4-fluoroacetanilide synthesis method | |
| CN113880790A (en) | Phase transfer catalytic synthesis method of 3, 4-epoxy cyclohexyl methyl-3 ',4' -epoxy cyclohexyl formic ether | |
| CN112679342A (en) | Preparation method of trans, trans-4, 4' -dicyclohexyl dicarboxylic acid | |
| JPH013139A (en) | Method for purifying tetrabromubisphenol A | |
| JPH0959268A (en) | Production of acrylic acid or methacrylic acid glycidyl ester | |
| CN114453032A (en) | Modified ion exchange resin, preparation method thereof and application thereof in polyhydric alcohol dehydration reaction | |
| JPH0725821A (en) | New solvent and its production | |
| CN113583234B (en) | Preparation method of double-end methacrylate-based polyphenyl ether | |
| CN107501553A (en) | A kind of preparation method of the polyphenylene sulfide of no catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221205 Address after: 710000 Room 203, Linjian Market, Fengcheng 8th Road, Xi'an Economic and Technological Development Zone, Shaanxi Province Applicant after: Zhilun Ultrapure Epoxy Resin (Xi'an) Co.,Ltd. Address before: 710000 Hubin Garden community, No. 3, Huanhu North Road, Weiyang District, Xi'an City, Shaanxi Province Applicant before: Du Biao |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 710000 Room 203, Linjian Market, Fengcheng 8th Road, Xi'an Economic and Technological Development Zone, Shaanxi Province Patentee after: Zhilun New Materials Technology (Xi'an) Co.,Ltd. Country or region after: China Address before: 710000 Room 203, Linjian Market, Fengcheng 8th Road, Xi'an Economic and Technological Development Zone, Shaanxi Province Patentee before: Zhilun Ultrapure Epoxy Resin (Xi'an) Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |