CN112206819A - Catalyst for allyl polyether end capping and preparation method thereof - Google Patents
Catalyst for allyl polyether end capping and preparation method thereof Download PDFInfo
- Publication number
- CN112206819A CN112206819A CN202011049147.1A CN202011049147A CN112206819A CN 112206819 A CN112206819 A CN 112206819A CN 202011049147 A CN202011049147 A CN 202011049147A CN 112206819 A CN112206819 A CN 112206819A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- allyl polyether
- copper sulfate
- anhydrous copper
- parts
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 229920000570 polyether Polymers 0.000 title claims abstract description 43
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 41
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 54
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 54
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 41
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 41
- 239000001119 stannous chloride Substances 0.000 claims abstract description 41
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 41
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000292 calcium oxide Substances 0.000 claims abstract description 35
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims abstract description 32
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 64
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 238000007710 freezing Methods 0.000 claims description 15
- 230000008014 freezing Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical group CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 5
- 102000004190 Enzymes Human genes 0.000 claims description 5
- 108090000790 Enzymes Proteins 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000010257 thawing Methods 0.000 claims description 5
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010981 drying operation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 43
- 230000032050 esterification Effects 0.000 abstract description 17
- 238000005886 esterification reaction Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 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 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 5
- 229910001504 inorganic chloride Inorganic materials 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000000227 grinding Methods 0.000 description 6
- 241000530268 Lycaena heteronea Species 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 231100000956 nontoxicity Toxicity 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for end capping of allyl polyether and a preparation method thereof, belonging to the field of end capping of allyl polyether. The catalyst for end capping allyl polyether mainly comprises the following raw materials: ferric chloride; stannous chloride; sodium bisulfate; anhydrous copper sulfate; a sulfur catalyst; calcium oxide; activated carbon; the calcium oxide is added into the catalyst, so that the moisture in the reaction can be absorbed, the absorption of moisture of ferric trichloride and stannous chloride is prevented, the heat is released after the calcium oxide absorbs the water, the temperature of the catalyst during the reaction is improved, the activity of the catalyst is improved, anhydrous copper sulfate crystals are separated out by heating the blue copperas, and the catalytic effect of the anhydrous copper sulfate on the esterification end capping of allyl polyether is improved; the active carbon is added into the catalyst, so that harmful gases generated in the reaction can be collected, and the catalyst can be used as a carrier of the catalyst, so that the catalytic effect of the catalyst is improved.
Description
Technical Field
The invention relates to the technical field of allyl polyether end capping, in particular to a catalyst for allyl polyether end capping and a preparation method thereof.
Background
Allyl polyethers are monofunctional polyethers prepared by homopolymerization, block polymerization or random polymerization of allyl alcohol as initiator with Ethylene Oxide (EO) or Propylene Oxide (PO), and are valued for their modification of the polyethers by the addition of reactive groups to the double bond.
In the reaction, a catalyst is often added to promote the allyl polyether end capping, for example, an inorganic chloride catalyst, a sulfate catalyst and a lipase catalysis synthetic ester catalyst are added, but the inorganic chloride catalyst is easy to absorb moisture, is not easy to decompose and store, and is further inconvenient to add inorganic chloride into the reaction, and the sulfate catalyst has low activity and poor promotion effect on the allyl polyether end capping.
Disclosure of Invention
The invention aims to solve the problems that a catalyst is often added to promote the allyl polyether end capping to be carried out in a reaction, such as an inorganic chloride catalyst, a sulfate catalyst and a lipase catalysis synthetic ester catalyst are added, but the inorganic chloride catalyst is easy to absorb moisture, is not easy to decompose and store, is further inconvenient to add inorganic chloride into the reaction, and the sulfate catalyst is low in activity and poor in effect of promoting the allyl polyether end capping, and provides the catalyst for the allyl polyether end capping and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the catalyst for end capping allyl polyether mainly comprises the following raw materials: ferric chloride; stannous chloride; sodium bisulfate; anhydrous copper sulfate; a sulfur catalyst; calcium oxide; activated carbon.
Preferably, the raw materials have the following component ratio: ferric chloride: 10-15 parts; stannous chloride: 2-8 parts; sodium hydrogen sulfate: 3-7 parts; anhydrous copper sulfate: 5-15 parts; sulfur catalyst: 1-5 parts; calcium oxide: 5-10 parts; activated carbon: and 20 parts.
Preferably, the sulphur catalyst is toluene sulphonic acid and/or sulphamic acid.
A preparation method of a catalyst for allyl polyether end capping mainly comprises the following steps:
s1, preparing calcium oxide solid powder;
s2, drying and refining ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst;
s3, putting the processed ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate, sulfur catalyst and calcium oxide into a mixer for mixing to obtain a mixture;
s4, preparing granular activated carbon;
and S5, adding the mixed mixture into granular activated carbon, and mixing to obtain the catalyst.
Preferably, the preparation of the calcium oxide solid powder in step S1 mainly comprises the following steps:
A. pretreatment: immersing shell powder containing calcium carbonate in deionized water, adding an enzyme preparation, performing enzymolysis treatment at 30-35 ℃ for 60-100 min, filtering, and taking an ethanol solution to clean filter residues to obtain high-purity calcium carbonate;
B. salinization and freezing treatment: adding 15-20 parts by weight of sodium chloride solution into high-purity calcium carbonate, treating for 10-20 min under the condition that the ultrasonic frequency is 50kHz, putting into a freezing chamber, and freezing for 20h at-20 to-34 ℃ to obtain treated calcium carbonate;
C. calcining treatment: and (3) placing the treated calcium carbonate into a muffle furnace, calcining the calcium carbonate, performing superfine treatment, and storing in an environment at 4-7 ℃ to obtain calcium oxide.
Preferably, the calcination conditions for calcium carbonate in step C are: heating to 500 deg.C at a speed of 15 deg.C/min, maintaining at constant temperature for 0.5h, heating to 900 deg.C at a speed of 25 deg.C/min, calcining for 5h, cooling to 500 deg.C at a speed of 40 deg.C/min, and naturally thawing to room temperature.
Preferably, the drying operation in step S2 is: and (3) putting the ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst into a dryer for drying, wherein the drying temperature is 100 ℃ and 150 ℃, and the drying time is 2-5 h.
Preferably, the refining operation in step S2 is: adding the dried ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and sulfur catalyst into a grinder to grind the membrane, screening by a 175-mesh and 225-mesh screen, and taking the screened particles for later use.
Preferably, the operation of preparing the granular activated carbon in the step S4 is mainly as follows: mixing the coal particles with ferrocene, and activating at high temperature to obtain the granular activated carbon.
Preferably, the mixer in step S3 is a three-dimensional mixer.
Compared with the prior art, the invention provides a catalyst for end capping of allyl polyether and a preparation method thereof, and the catalyst has the following beneficial effects:
according to the catalyst for the termination of the allyl polyether and the preparation method thereof, ferric trichloride and stannous chloride are added into the catalyst, the catalyst is an inorganic chloride catalyst, and in the termination of the allyl polyether esterification, the catalyst is stable in property, non-toxic, small in corrosion to equipment and environmental pollution, convenient in catalytic esterification operation, mild in reaction and short in reaction time;
the anhydrous copper sulfate and the sodium bisulfate are added into the catalyst, the catalyst is a sulfate catalyst, and is separated from a reaction system in the esterification and termination of the allyl polyether, so that the operation is convenient, and meanwhile, the catalyst is cheap and easy to obtain, the reaction time is short, and the equipment cannot be corroded;
the anhydrous copper sulfate can absorb moisture in the reaction during the reaction to prevent the absorption of moisture of ferric trichloride and stannous chloride, the catalyst is separated and taken out after the reaction, and the anhydrous copper sulfate becomes blue copper sulfate after meeting water to judge the amount of moisture in the catalyst during the reaction;
the calcium oxide is added into the catalyst, so that the moisture in the reaction can be absorbed, the absorption of moisture of ferric trichloride and stannous chloride is prevented, the heat is released after the calcium oxide absorbs the water, the temperature of the catalyst during the reaction is increased, the activity of the catalyst is improved, anhydrous copper sulfate crystals are separated out by heating the blue copperas, and the catalytic effect of the anhydrous copper sulfate on the esterification end capping of allyl polyether is improved;
the active carbon is added into the catalyst, so that harmful gases generated in the reaction can be collected, and the catalyst can be used as a carrier of the catalyst, so that the catalytic effect of the catalyst is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like, indicate orientations and positional relationships for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
Example 1:
a catalyst for end capping allyl polyether and its preparing process, iron trichloride: 10 parts of (A); stannous chloride: 2 parts of (1); sodium hydrogen sulfate: 3 parts of a mixture; anhydrous copper sulfate: 5 parts of a mixture; sulfur catalyst: 1 part; calcium oxide: 5 parts of a mixture; activated carbon: 20 parts, wherein the sulfur catalyst is toluenesulfonic acid: 1:1 of sulfamic acid;
in the preparation of the catalyst, calcium oxide solid powder is prepared:
the first step of pretreatment: immersing shell powder containing calcium carbonate in deionized water, adding an enzyme preparation, performing enzymolysis treatment at 30-35 ℃ for 60-100 min, filtering, and taking an ethanol solution to clean filter residues to obtain high-purity calcium carbonate;
and a second salinization and freezing treatment: adding 15-20 parts by weight of sodium chloride solution into high-purity calcium carbonate, treating for 10-20 min under the condition that the ultrasonic frequency is 50kHz, putting into a freezing chamber, and freezing for 20h at-20 to-34 ℃ to obtain treated calcium carbonate;
the third step of calcination treatment: placing the treated calcium carbonate into a muffle furnace, calcining the calcium carbonate, heating to 500 ℃ at a speed of 15 ℃/min, keeping the temperature for 0.5h, heating to 900 ℃ at a speed of 25 ℃/min, calcining for 5h, cooling to 500 ℃ at a speed of 40 ℃/min, naturally thawing to room temperature, performing superfine treatment, and storing in an environment at 4-7 ℃ to obtain calcium oxide powder;
then drying and refining ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst:
during drying, putting ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst into a dryer for drying, wherein the drying temperature is 100 ℃ and 150 ℃, and the drying time is 2-5 h;
during refining, the dried ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and sulfur catalyst are added into a grinding machine for membrane grinding, screening is carried out through a screen with 175-mesh and 225-mesh, and the screened particles are taken for standby;
then putting the treated ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate, a sulfur catalyst and calcium oxide into a three-dimensional mixer for mixing to obtain a mixture;
and preparing granular activated carbon: mixing coal particles with ferrocene, and then activating at high temperature to obtain granular activated carbon;
finally, adding the mixed mixture into granular activated carbon for mixing to obtain a catalyst;
by adding ferric trichloride and stannous chloride into the catalyst, the catalyst is an inorganic chloride catalyst, and has the advantages of stable property, no toxicity, little corrosion to equipment and environmental pollution in the esterification end capping of allyl polyether, convenient catalytic esterification operation, mild reaction and short reaction time;
the anhydrous copper sulfate and the sodium bisulfate are added into the catalyst, the catalyst is a sulfate catalyst, and is separated from a reaction system in the esterification and termination of the allyl polyether, so that the operation is convenient, and meanwhile, the catalyst is cheap and easy to obtain, the reaction time is short, and the equipment cannot be corroded;
the anhydrous copper sulfate can absorb moisture in the reaction during the reaction to prevent the absorption of moisture of ferric trichloride and stannous chloride, the catalyst is separated and taken out after the reaction, and the anhydrous copper sulfate becomes blue copper sulfate after meeting water to judge the amount of moisture in the catalyst during the reaction;
the calcium oxide is added into the catalyst, so that the moisture in the reaction can be absorbed, the absorption of moisture of ferric trichloride and stannous chloride is prevented, the heat is released after the calcium oxide absorbs the water, the temperature of the catalyst during the reaction is increased, and then anhydrous copper sulfate crystals are separated out by heating the blue copperas, so that the catalytic effect of the anhydrous copper sulfate on the esterification end capping of allyl polyether is improved;
the active carbon is added into the catalyst, so that harmful gases generated in the reaction can be collected, and the catalyst can be used as a carrier of the catalyst, so that the catalytic effect of the catalyst is improved.
Example 2:
a catalyst for end capping allyl polyether and its preparing process, iron trichloride: 12.5 parts; stannous chloride: 5 parts of a mixture; sodium hydrogen sulfate: 5 parts of a mixture; anhydrous copper sulfate: 10 parts of (A); sulfur catalyst: 2.5 parts; calcium oxide: 7.5 parts; activated carbon: 20 parts, wherein the sulfur catalyst is toluenesulfonic acid: 1:1 of sulfamic acid;
in the preparation of the catalyst, calcium oxide solid powder is prepared:
the first step of pretreatment: immersing shell powder containing calcium carbonate in deionized water, adding an enzyme preparation, performing enzymolysis treatment at 30-35 ℃ for 60-100 min, filtering, and taking an ethanol solution to clean filter residues to obtain high-purity calcium carbonate;
and a second salinization and freezing treatment: adding 15-20 parts by weight of sodium chloride solution into high-purity calcium carbonate, treating for 10-20 min under the condition that the ultrasonic frequency is 50kHz, putting into a freezing chamber, and freezing for 20h at-20 to-34 ℃ to obtain treated calcium carbonate;
the third step of calcination treatment: placing the treated calcium carbonate into a muffle furnace, calcining the calcium carbonate, heating to 500 ℃ at a speed of 15 ℃/min, keeping the temperature for 0.5h, heating to 900 ℃ at a speed of 25 ℃/min, calcining for 5h, cooling to 500 ℃ at a speed of 40 ℃/min, naturally thawing to room temperature, performing superfine treatment, and storing in an environment at 4-7 ℃ to obtain calcium oxide powder;
then drying and refining ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst:
during drying, putting ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst into a dryer for drying, wherein the drying temperature is 100 ℃ and 150 ℃, and the drying time is 2-5 h;
during refining, the dried ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and sulfur catalyst are added into a grinding machine for membrane grinding, screening is carried out through a screen with 175-mesh and 225-mesh, and the screened particles are taken for standby;
then putting the treated ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate, a sulfur catalyst and calcium oxide into a three-dimensional mixer for mixing to obtain a mixture;
and preparing granular activated carbon: mixing coal particles with ferrocene, and then activating at high temperature to obtain granular activated carbon;
finally, adding the mixed mixture into granular activated carbon for mixing to obtain a catalyst;
by adding ferric trichloride and stannous chloride into the catalyst, the catalyst is an inorganic chloride catalyst, and has the advantages of stable property, no toxicity, little corrosion to equipment and environmental pollution in the esterification end capping of allyl polyether, convenient catalytic esterification operation, mild reaction and short reaction time;
the anhydrous copper sulfate and the sodium bisulfate are added into the catalyst, the catalyst is a sulfate catalyst, and is separated from a reaction system in the esterification and termination of the allyl polyether, so that the operation is convenient, and meanwhile, the catalyst is cheap and easy to obtain, the reaction time is short, and the equipment cannot be corroded;
the anhydrous copper sulfate can absorb moisture in the reaction during the reaction to prevent the absorption of moisture of ferric trichloride and stannous chloride, the catalyst is separated and taken out after the reaction, and the anhydrous copper sulfate becomes blue copper sulfate after meeting water to judge the amount of moisture in the catalyst during the reaction;
the calcium oxide is added into the catalyst, so that the moisture in the reaction can be absorbed, the absorption of moisture of ferric trichloride and stannous chloride is prevented, the heat is released after the calcium oxide absorbs the water, the temperature of the catalyst during the reaction is increased, and then anhydrous copper sulfate crystals are separated out by heating the blue copperas, so that the catalytic effect of the anhydrous copper sulfate on the esterification end capping of allyl polyether is improved;
the active carbon is added into the catalyst, so that harmful gases generated in the reaction can be collected, and the catalyst can be used as a carrier of the catalyst, so that the catalytic effect of the catalyst is improved.
Example 3:
a catalyst for end capping allyl polyether and its preparing process, iron trichloride: 15 parts of (1); stannous chloride: 8 parts of a mixture; sodium hydrogen sulfate: 7 parts; anhydrous copper sulfate: 15 parts of (1); sulfur catalyst: 5 parts of a mixture; calcium oxide: 10 parts of (A); activated carbon: 20 parts, wherein the sulfur catalyst is toluenesulfonic acid: 1:1 of sulfamic acid;
in the preparation of the catalyst, calcium oxide solid powder is prepared:
the first step of pretreatment: immersing shell powder containing calcium carbonate in deionized water, adding an enzyme preparation, performing enzymolysis treatment at 30-35 ℃ for 60-100 min, filtering, and taking an ethanol solution to clean filter residues to obtain high-purity calcium carbonate;
and a second salinization and freezing treatment: adding 15-20 parts by weight of sodium chloride solution into high-purity calcium carbonate, treating for 10-20 min under the condition that the ultrasonic frequency is 50kHz, putting into a freezing chamber, and freezing for 20h at-20 to-34 ℃ to obtain treated calcium carbonate;
the third step of calcination treatment: placing the treated calcium carbonate into a muffle furnace, calcining the calcium carbonate, heating to 500 ℃ at a speed of 15 ℃/min, keeping the temperature for 0.5h, heating to 900 ℃ at a speed of 25 ℃/min, calcining for 5h, cooling to 500 ℃ at a speed of 40 ℃/min, naturally thawing to room temperature, performing superfine treatment, and storing in an environment at 4-7 ℃ to obtain calcium oxide powder;
then drying and refining ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst:
during drying, putting ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst into a dryer for drying, wherein the drying temperature is 100 ℃ and 150 ℃, and the drying time is 2-5 h;
during refining, the dried ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and sulfur catalyst are added into a grinding machine for membrane grinding, screening is carried out through a screen with 175-mesh and 225-mesh, and the screened particles are taken for standby;
then putting the treated ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate, a sulfur catalyst and calcium oxide into a three-dimensional mixer for mixing to obtain a mixture;
and preparing granular activated carbon: mixing coal particles with ferrocene, and then activating at high temperature to obtain granular activated carbon;
finally, adding the mixed mixture into granular activated carbon for mixing to obtain a catalyst;
by adding ferric trichloride and stannous chloride into the catalyst, the catalyst is an inorganic chloride catalyst, and has the advantages of stable property, no toxicity, little corrosion to equipment and environmental pollution in the esterification end capping of allyl polyether, convenient catalytic esterification operation, mild reaction and short reaction time;
the anhydrous copper sulfate and the sodium bisulfate are added into the catalyst, the catalyst is a sulfate catalyst, and is separated from a reaction system in the esterification and termination of the allyl polyether, so that the operation is convenient, and meanwhile, the catalyst is cheap and easy to obtain, the reaction time is short, and the equipment cannot be corroded;
the anhydrous copper sulfate can absorb moisture in the reaction during the reaction to prevent the absorption of moisture of ferric trichloride and stannous chloride, the catalyst is separated and taken out after the reaction, and the anhydrous copper sulfate becomes blue copper sulfate after meeting water to judge the amount of moisture in the catalyst during the reaction;
the calcium oxide is added into the catalyst, so that the moisture in the reaction can be absorbed, the absorption of moisture of ferric trichloride and stannous chloride is prevented, the heat is released after the calcium oxide absorbs the water, the temperature of the catalyst during the reaction is increased, and then anhydrous copper sulfate crystals are separated out by heating the blue copperas, so that the catalytic effect of the anhydrous copper sulfate on the esterification end capping of allyl polyether is improved;
the active carbon is added into the catalyst, so that harmful gases generated in the reaction can be collected, and the catalyst can be used as a carrier of the catalyst, so that the catalytic effect of the catalyst is improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The catalyst for end capping of allyl polyether is characterized by mainly comprising the following raw materials:
ferric chloride;
stannous chloride;
sodium bisulfate;
anhydrous copper sulfate;
a sulfur catalyst;
calcium oxide;
activated carbon.
2. The allyl polyether end capping catalyst according to claim 1, wherein the raw materials comprise:
ferric chloride: 10-15 parts;
stannous chloride: 2-8 parts;
sodium hydrogen sulfate: 3-7 parts;
anhydrous copper sulfate: 5-15 parts;
sulfur catalyst: 1-5 parts;
calcium oxide: 5-10 parts;
activated carbon: and 20 parts.
3. The allyl polyether capping catalyst of claim 1, wherein the sulfur catalyst is toluene sulfonic acid and/or sulfamic acid.
4. A method for preparing a catalyst for allyl polyether termination, which is characterized in that the catalyst for allyl polyether termination according to any one of claims 1 to 3 is used, and mainly comprises the following steps:
s1, preparing calcium oxide solid powder;
s2, drying and refining ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst;
s3, putting the processed ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate, sulfur catalyst and calcium oxide into a mixer for mixing to obtain a mixture;
s4, preparing granular activated carbon;
and S5, adding the mixed mixture into granular activated carbon, and mixing to obtain the catalyst.
5. The method of claim 4, wherein the step of preparing solid calcium oxide powder in step S1 comprises the steps of:
A. pretreatment: immersing shell powder containing calcium carbonate in deionized water, adding an enzyme preparation, performing enzymolysis treatment at 30-35 ℃ for 60-100 min, filtering, and taking an ethanol solution to clean filter residues to obtain high-purity calcium carbonate;
B. salinization and freezing treatment: adding 15-20 parts by weight of sodium chloride solution into high-purity calcium carbonate, treating for 10-20 min under the condition that the ultrasonic frequency is 50kHz, putting into a freezing chamber, and freezing for 20h at-20 to-34 ℃ to obtain treated calcium carbonate;
C. calcining treatment: and (3) placing the treated calcium carbonate into a muffle furnace, calcining the calcium carbonate, performing superfine treatment, and storing in an environment at 4-7 ℃ to obtain calcium oxide.
6. The method of claim 5, wherein the calcium carbonate is calcined in step C under the following conditions: heating to 500 deg.C at a speed of 15 deg.C/min, maintaining at constant temperature for 0.5h, heating to 900 deg.C at a speed of 25 deg.C/min, calcining for 5h, cooling to 500 deg.C at a speed of 40 deg.C/min, and naturally thawing to room temperature.
7. The method for preparing the allyl polyether end-capping catalyst according to claim 4, wherein the drying operation in the step S2 is: and (3) putting the ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and a sulfur catalyst into a dryer for drying, wherein the drying temperature is 100 ℃ and 150 ℃, and the drying time is 2-5 h.
8. The method for preparing the allyl polyether end-capping catalyst according to claim 4, wherein the refining operation in the step S2 is: adding the dried ferric trichloride, stannous chloride, sodium bisulfate, anhydrous copper sulfate and sulfur catalyst into a grinder to grind the membrane, screening by a 175-mesh and 225-mesh screen, and taking the screened particles for later use.
9. The method of claim 4, wherein the step S4 of preparing the granular activated carbon comprises the following steps: mixing the coal particles with ferrocene, and activating at high temperature to obtain the granular activated carbon.
10. The method for producing an allyl polyether terminal-blocking catalyst according to claim 4, wherein the mixer in step S3 is a three-dimensional mixer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011049147.1A CN112206819A (en) | 2020-09-29 | 2020-09-29 | Catalyst for allyl polyether end capping and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011049147.1A CN112206819A (en) | 2020-09-29 | 2020-09-29 | Catalyst for allyl polyether end capping and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112206819A true CN112206819A (en) | 2021-01-12 |
Family
ID=74052092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011049147.1A Pending CN112206819A (en) | 2020-09-29 | 2020-09-29 | Catalyst for allyl polyether end capping and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112206819A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1504493A (en) * | 2002-11-28 | 2004-06-16 | 中国石化上海石油化工股份有限公司 | Method for preparing alkyl end capping polyether using alkylsulfate as end capping reagent |
| CN101735444A (en) * | 2008-11-10 | 2010-06-16 | 南京林业大学 | Esterification and termination synthesis method of allyl polyether |
| CN103193973A (en) * | 2013-04-22 | 2013-07-10 | 苏州思德新材料科技有限公司 | End capping method of allyl polyether |
| CN106243344A (en) * | 2016-08-19 | 2016-12-21 | 浙江皇马科技股份有限公司 | A kind of epoxy radicals end capped polyether continuous open loop production technology |
| US20160367977A1 (en) * | 2015-06-19 | 2016-12-22 | Saudi Arabian Oil Company | Antifouling oligomerization catalyst systems |
| CN107720798A (en) * | 2017-09-30 | 2018-02-23 | 广西华洋矿源材料有限公司 | The preparation method of active calcium oxide |
| US20180271191A1 (en) * | 2017-03-27 | 2018-09-27 | Shujun Sang | High-elasticity polyurethane material |
-
2020
- 2020-09-29 CN CN202011049147.1A patent/CN112206819A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1504493A (en) * | 2002-11-28 | 2004-06-16 | 中国石化上海石油化工股份有限公司 | Method for preparing alkyl end capping polyether using alkylsulfate as end capping reagent |
| CN101735444A (en) * | 2008-11-10 | 2010-06-16 | 南京林业大学 | Esterification and termination synthesis method of allyl polyether |
| CN103193973A (en) * | 2013-04-22 | 2013-07-10 | 苏州思德新材料科技有限公司 | End capping method of allyl polyether |
| US20160367977A1 (en) * | 2015-06-19 | 2016-12-22 | Saudi Arabian Oil Company | Antifouling oligomerization catalyst systems |
| CN106243344A (en) * | 2016-08-19 | 2016-12-21 | 浙江皇马科技股份有限公司 | A kind of epoxy radicals end capped polyether continuous open loop production technology |
| US20180271191A1 (en) * | 2017-03-27 | 2018-09-27 | Shujun Sang | High-elasticity polyurethane material |
| CN107720798A (en) * | 2017-09-30 | 2018-02-23 | 广西华洋矿源材料有限公司 | The preparation method of active calcium oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112456491B (en) | Production process of environment-friendly regenerated activated carbon | |
| CN101962184A (en) | Method for preparing active carbon by mechanical-chemical method | |
| CN104944425A (en) | Preparation method of active carbon | |
| CN1057065C (en) | Preparation of superhigh specific surface area active carbon | |
| CN105236407A (en) | Double-layer capacitor electrode spherical active carbon material preparation method | |
| CN110026203A (en) | Utilize the method for rare-earth tailing preparation SCR denitration | |
| CN101654232A (en) | Method for adsorbing and purifying PH3 under reducing condition | |
| CN111589415A (en) | Preparation method of active carbon loaded with zinc oxide in situ | |
| CN107983108B (en) | Preparation method of special sulfur fixing agent for flue gas desulfurization | |
| CN114832838A (en) | Metal/sulfur-persulfate-loaded biochar composite material and preparation and application thereof | |
| CN108314167B (en) | Waste acid removing composite alkali and preparation method thereof | |
| CN112206819A (en) | Catalyst for allyl polyether end capping and preparation method thereof | |
| CN113210022A (en) | Preparation method of Cu-attapulgite-chitosan chelate microsphere catalyst applied to catalytic wet oxidation | |
| CN117101689A (en) | Catalyst for hexafluoropropane preparation, hexafluoropropane and preparation method thereof | |
| CN101816928A (en) | Method for preparing coke-powder-based carbon adsorbing material by using waste coke powder | |
| CN116673028A (en) | Catalyst for purifying flue gas of rubber asphalt and preparation method thereof | |
| CN106732522A (en) | The preparation method of carrying transition metal oxide catalyst | |
| CN114377705B (en) | Fly ash-based phosphorus-doped carbon dot photocatalytic material and preparation method and application thereof | |
| CN110252375A (en) | A kind of iron, nitrogen, the Titanium dioxide/active carbon compound of cobalt codope, preparation method and as photocatalyst applications | |
| CN110605106A (en) | Regeneration method of waste mercury catalyst activated carbon after harmless treatment | |
| CN113786703B (en) | Method for efficiently adsorbing and purifying flue gas by using microwave outfield and industrial waste residues | |
| CN101422737B (en) | Preparation method of catalyst TP201 special for dephosphorization of phosphor tail-gas | |
| GB2619195A (en) | Preparation method for carbon dioxide capture agent, and application thereof | |
| CN112547046B (en) | Preparation method of environment-friendly denitration catalyst based on vanadium-titanium slag | |
| CN104085889A (en) | Preparation method of granular activated carbon |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210112 |
|
| WD01 | Invention patent application deemed withdrawn after publication |