CN118002202B - Catalyst for catalytic synthesis of dimethyl thiotoluene diamine, and preparation method and application thereof - Google Patents
Catalyst for catalytic synthesis of dimethyl thiotoluene diamine, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004964 aerogel Substances 0.000 claims abstract description 127
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 83
- 239000002131 composite material Substances 0.000 claims abstract description 82
- 239000000843 powder Substances 0.000 claims abstract description 81
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 79
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000536 complexating effect Effects 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 128
- 238000003756 stirring Methods 0.000 claims description 69
- 238000001035 drying Methods 0.000 claims description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 235000019441 ethanol Nutrition 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 24
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 18
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 17
- -1 alkyl orthosilicate Chemical compound 0.000 claims description 17
- 239000004246 zinc acetate Substances 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 12
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 11
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 10
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical group Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 150000000918 Europium Chemical class 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 150000002603 lanthanum Chemical class 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 7
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical group [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 4
- 241001112258 Moca Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The invention provides a catalyst for catalytic synthesis of dimethyl thiotoluene diamine and a preparation method and application thereof, and belongs to the technical field of organic catalysis. Preparing SiO 2/Al2O3/ZnO composite aerogel powder, doping La/Eu oxide, carrying out ring-opening grafting reaction on the modified surface and polyvinyl alcohol after KH560 modification, and then complexing tin metal to obtain the catalyst for catalytic synthesis of dimethyl thiotoluenediamine. The catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine has the advantages of simple preparation method, mild condition, easy preservation, repeated use, high catalytic activity, strong selectivity and wide application prospect, and overcomes the problem that a high polymer catalyst is easy to expand, and the catalyst can effectively reduce the reaction activation energy, so that the synthetic reaction condition of the dimethyl thiotoluene diamine is milder.
Description
Technical Field
The invention relates to the technical field of organic catalysis, in particular to a catalyst for catalyzing and synthesizing dimethyl thiotoluene diamine, and a preparation method and application thereof.
Background
In the processing and shaping of polyurethane elastomers, a curing agent which has both chain extension and crosslinking functions must be added, and the curing agent which has been used most successfully for decades is 3,3 '-dichloro-4, 4' -diamino-diphenylmethane (MOCA). While the physical mechanical properties of elastomers made with MOCA are best, the deadly weakness is carcinogenicity, and the U.S. government has mandated the termination of MOCA use in polyurethanes. For this reason, new curing agents have been studied in competition in countries around the world, but none have achieved the ideal results. In 1987, the American Ethyl company research found that dimethyl thiotoluenediamine (DMTDA) was a curing agent promising for replacing MOCA.
The dimethyl thiotoluene diamine is produced by reacting diaminotoluene with alkylation reagent dimethyl disulfide in the presence of Lewis acid catalyst at 100-200 ℃ and under normal pressure to 6.9MPa, and after the reaction, the reaction product is separated by vacuum rectification, and the disadvantage is that the loss of dimethyl disulfide is great, the reaction product has high temperature and contains some water-soluble impurities such as diaminotoluene and some organic salt substances.
Therefore, a high-activity catalyst is needed to be found, which can improve the reaction yield, reduce the reaction activation energy and reduce the generation of impurities.
Disclosure of Invention
The invention aims to provide a catalyst for catalyzing and synthesizing dimethyl thiotoluene diamine, and a preparation method and application thereof, wherein the preparation method is simple, mild in condition, easy to store, capable of being repeatedly used, high in catalytic activity and strong in selectivity, and can effectively reduce the reaction activation energy, so that the synthetic reaction condition of dimethyl thiotoluene diamine is milder, and the catalyst has a wide application prospect.
The technical scheme of the invention is realized as follows:
The invention provides a preparation method of a catalyst for catalytic synthesis of dimethyl thiotoluene diamine, which is characterized in that SiO 2/Al2O3/ZnO composite aerogel powder is prepared, la/Eu oxide is doped, after KH560 modification is carried out on the surface, ring-opening grafting reaction is carried out on the surface and polyvinyl alcohol, then tin metal is complexed, and the catalyst for catalytic synthesis of dimethyl thiotoluene diamine is prepared.
As a further improvement of the invention, the method comprises the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving alkyl orthosilicate in ethanol, adding water and acetic acid, heating and stirring for reacting for a first time period, then adding aluminum alkoxide and zinc acetate, stirring for a second time period, dripping ammonia water for regulating the pH value, drying to form gel, aging, adding the gel into a modified liquid for soaking, then using ethanol for solvent replacement, drying and crushing to obtain SiO 2/Al2O3/ZnO composite aerogel powder;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding the SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into water, adding lanthanum salt and europium salt, adding citric acid, stirring and mixing uniformly, volatilizing a solvent, calcining, washing and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder;
S3, modification: adding the La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S2 into ethanol, adding KH560, heating and stirring for reaction, filtering, washing and drying to obtain modified aerogel;
s4, ring opening: adding the modified aerogel prepared in the step S3 and polyvinyl alcohol into 1, 4-dioxane, adding boron trifluoride diethyl ether, heating, stirring and carrying out ring opening reaction to obtain polyhydroxy aerogel;
S5, complexing: and (3) adding the polyhydroxy aerogel prepared in the step (S4) into water, adding tin salt, stirring and mixing uniformly, filtering, washing and drying to obtain the catalyst for catalytic synthesis of the dimethyl thiotoluene diamine.
As a further improvement of the invention, in the step S1, the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, the aluminum alkoxide is selected from aluminum sec-butoxide or aluminum isopropoxide, the mass ratio of the alkyl orthosilicate to the aluminum alkoxide to the zinc acetate to the ethanol to the water to the acetic acid is 10-15:5-7:4-6:70-100:12-15:3-5, the temperature of the heating and stirring reaction is 80-90 ℃, the first time period is 5-7h, the second time period is 10-20min, the pH value is 8-9, the temperature of the gel formed by drying is 55-65 ℃ for 1-2h, the aging time is 2-3h, the modifying liquid is a mixed liquid of trimethylchlorosilane and absolute ethanol according to the mass ratio of 1-2:15-20, and the soaking time is 5-7h.
As a further improvement of the invention, in the step S2, the mass ratio of the SiO 2/Al2O3/ZnO composite aerogel powder to the lanthanum salt to the europium salt to the citric acid is 100:3-5:2-4:7-10, the lanthanum salt is at least one of lanthanum chloride, lanthanum sulfate and lanthanum nitrate, the europium salt is europium chloride, the calcining temperature is 300-400 ℃ and the calcining time is 0.5-1h.
As a further improvement of the invention, in the step S3, the mass ratio of the La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder to KH560 is 10:1-2, the temperature of the heating and stirring reaction is 40-50 ℃ and the time is 2-4h.
As a further improvement of the invention, in the step S4, the mass ratio of the modified aerogel to the polyvinyl alcohol to the boron trifluoride diethyl ether is 10:3-5:0.1-0.2, the polyvinyl alcohol is polyvinyl alcohol 400 or polyvinyl alcohol 1000, the temperature of the heating stirring ring-opening reaction is 90-100 ℃, and the time is 0.5-1h.
As a further improvement of the invention, the mass ratio of the polyhydroxy aerogel to the tin salt in the step S5 is 100:2.5-5, the tin salt is at least one selected from tin chloride, tin sulfate and tin nitrate, and the stirring and mixing time is 15-25min.
As a further improvement of the invention, the method specifically comprises the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 10-15 parts by weight of alkyl orthosilicate in 70-100 parts by weight of ethanol, adding 12-15 parts by weight of water and 3-5 parts by weight of acetic acid, heating to 80-90 ℃, stirring for reacting for 5-7 hours, then adding 5-7 parts by weight of aluminum alkoxide and 4-6 parts by weight of zinc acetate, stirring for 10-20 minutes, dripping ammonia water to adjust the pH value to 8-9, heating to 55-65 ℃ for drying for 1-2 hours to form gel, aging for 2-3 hours, adding the gel into a modified liquid, soaking for 5-7 hours, then replacing with ethanol, drying, and crushing to obtain SiO 2/Al2O3/ZnO composite aerogel powder;
The modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1-2:15-20;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 3-5 parts by weight of lanthanum salt and 2-4 parts by weight of europium salt, adding 7-10 parts by weight of citric acid, stirring and mixing uniformly, volatilizing a solvent, calcining at 300-400 ℃ for 0.5-1h, washing and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder;
S3, modification: adding 10 parts by weight of La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S2 into 100 parts by weight of ethanol, adding 1-2 parts by weight of KH560, heating to 40-50 ℃, stirring and reacting for 2-4 hours, filtering, washing and drying to prepare modified aerogel;
S4, ring opening: adding 10 parts by weight of the modified aerogel prepared in the step S3 and 3-5 parts by weight of polyvinyl alcohol into 100 parts by weight of 1, 4-dioxane, adding 0.1-0.2 part by weight of boron trifluoride diethyl ether, heating to 90-100 ℃, stirring and carrying out ring opening reaction for 0.5-1h to obtain polyhydroxy aerogel;
S5, complexing: adding 100 parts by weight of the polyhydroxy aerogel prepared in the step S4 into 200 parts by weight of water, adding 2.5-5 parts by weight of tin salt, stirring and mixing for 15-25min, filtering, washing and drying to obtain the catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine.
The invention further protects the catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine, which is prepared by the preparation method.
The invention further protects the application of the catalyst in catalytic synthesis of dimethyl thiotoluene diamine.
The invention has the following beneficial effects:
The skeleton and the holes of the aerogel material are both in the nanometer level, and the aerogel material has the advantages of three-dimensional reticular structure characteristics, high pore volume, large specific surface area and the like, and can provide rich catalytic sites when being used as a catalyst, so that the catalytic activity is greatly improved, but the aerogel has some problems such as low strength, high brittleness, hydrophilicity, easiness in pulverization and the like, and the practical application of the aerogel is severely limited. Meanwhile, the SiO 2/Al2O3/ZnO composite aerogel prepared by the method is different in hydrolysis rate and hydrolysis products of Si, al and Zn precursors, so that the SiO 2/Al2O3/ZnO composite aerogel can well obtain composite sol/gel by regulating and controlling the proportion of the Si, al and Zn precursors and a step-by-step hydrolysis method, and under the action of a modifier, a silicon source containing an elastic group is introduced into an aerogel framework, a pore structure is regulated, the neck area of aerogel nano particles is enhanced, the mechanical property of the aerogel is improved, the problems of low strength, high brittleness, hydrophilicity, easiness in pulverization and the like of the aerogel are solved, and the SiO 2/Al2O3/ZnO composite aerogel powder with high catalytic active sites and rich Al/Zn catalyst content is prepared. The Al 2O3/ZnO is combined, so that the dispersity of ZnO which is an active component can be improved, and the concentration of oxygen vacancies, the pore structure and the pore size of the surface can be modulated, so that the rapid generation of a reaction intermediate is realized.
The prepared SiO 2/Al2O3/ZnO composite aerogel powder is doped with La/Eu, and lanthanide metals La and Eu can have good effect of improving catalytic activity due to special outer-layer electron arrangement, and meanwhile, can cover the acid position of the outer surface, effectively inhibit isomerization reaction on the outer surface of a molecular sieve, so that the shape selectivity of the catalyst is obviously improved.
The surface of the prepared La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder is modified by KH560 with epoxy groups and is subjected to catalytic ring-opening grafting reaction with polyvinyl alcohol, so that the surface of the catalyst is provided with rich hydroxyl groups, sn ions can be loaded through complexation, and the catalytic activity is improved.
The catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine has the advantages of simple preparation method, mild condition, easy preservation, repeated use, high catalytic activity, strong selectivity and wide application prospect, and overcomes the problem that a high polymer catalyst is easy to expand, and the catalyst can effectively reduce the reaction activation energy, so that the synthetic reaction condition of the dimethyl thiotoluene diamine is milder.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a catalyst for catalytic synthesis of dimethyl thiotoluene diamine, which specifically comprises the following steps:
s1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 10 parts by weight of tetraethoxysilane in 70 parts by weight of ethanol, adding 12 parts by weight of water and 3 parts by weight of acetic acid, heating to 80 ℃, stirring and reacting for 5 hours, then adding 5 parts by weight of aluminum sec-butoxide and 4 parts by weight of zinc acetate, stirring for 10 minutes, dropwise adding ammonia water to adjust the pH value to 8, heating to 55 ℃ and drying for 1 hour to form gel, aging for 2 hours, adding the gel into a modified solution and soaking for 5 hours, then replacing the gel with ethanol, drying and crushing to prepare SiO 2/Al2O3/ZnO composite aerogel powder;
the modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1:15;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 3 parts by weight of lanthanum chloride and 2 parts by weight of europium chloride, adding 7 parts by weight of citric acid, stirring and mixing for 20min, volatilizing a solvent, calcining at 300 ℃ for 0.5h, washing and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder;
S3, modification: adding 10 parts by weight of La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S2 into 100 parts by weight of ethanol, adding 1 part by weight of KH560, heating to 40 ℃, stirring and reacting for 2 hours, filtering, washing and drying to prepare modified aerogel;
S4, ring opening: adding 10 parts by weight of the modified aerogel prepared in the step S3 and 3 parts by weight of polyvinyl alcohol 400 into 100 parts by weight of 1, 4-dioxane, adding 0.1 part by weight of boron trifluoride diethyl ether, heating to 90 ℃, and stirring for ring-opening reaction for 0.5h to prepare polyhydroxy aerogel;
s5, complexing: 100 parts by weight of the polyhydroxy aerogel prepared in the step S4 is added into 200 parts by weight of water, 2.5 parts by weight of stannic chloride is added, and the mixture is stirred and mixed for 15 minutes, filtered, washed and dried to prepare the catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine.
Example 2
The embodiment provides a preparation method of a catalyst for catalytic synthesis of dimethyl thiotoluene diamine, which specifically comprises the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 15 parts by weight of methyl orthosilicate in 100 parts by weight of ethanol, adding 15 parts by weight of water and 5 parts by weight of acetic acid, heating to 90 ℃, stirring and reacting for 7 hours, then adding 7 parts by weight of aluminum isopropoxide and 6 parts by weight of zinc acetate, stirring for 20 minutes, dripping ammonia water to adjust the pH value to 9, heating to 65 ℃ and drying for 2 hours to form gel, aging for 3 hours, adding the modified solution and soaking for 7 hours, then replacing the modified solution with ethanol, drying and crushing to prepare SiO 2/Al2O3/ZnO composite aerogel powder;
the modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 2:20;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 5 parts by weight of lanthanum sulfate and 4 parts by weight of europium chloride, adding 10 parts by weight of citric acid, stirring and mixing for 20min, volatilizing a solvent, calcining at 400 ℃ for 1h, washing and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder;
s3, modification: adding 10 parts by weight of La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S2 into 100 parts by weight of ethanol, adding 2 parts by weight of KH560, heating to 50 ℃, stirring and reacting for 4 hours, filtering, washing and drying to prepare modified aerogel;
S4, ring opening: adding 10 parts by weight of the modified aerogel prepared in the step S3 and 5 parts by weight of polyvinyl alcohol 400 into 100 parts by weight of 1, 4-dioxane, adding 0.2 part by weight of boron trifluoride diethyl ether, heating to 100 ℃, and stirring for ring-opening reaction for 1h to obtain polyhydroxy aerogel;
S5, complexing: 100 parts by weight of the polyhydroxy aerogel prepared in the step S4 is added into 200 parts by weight of water, 5 parts by weight of tin sulfate is added, and the mixture is stirred and mixed for 25 minutes, filtered, washed and dried to prepare the catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine.
Example 3
The embodiment provides a preparation method of a catalyst for catalytic synthesis of dimethyl thiotoluene diamine, which specifically comprises the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 12 parts by weight of tetraethoxysilane in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, then adding 6 parts by weight of aluminum isopropoxide and 5 parts by weight of zinc acetate, stirring for 15 minutes, dripping ammonia water to adjust the pH value to 8.5, heating to 60 ℃ and drying for 1.5 hours to form gel, aging for 2.5 hours, adding the gel into a modified solution and soaking for 6 hours, then replacing the gel with ethanol, drying and crushing to prepare SiO 2/Al2O3/ZnO composite aerogel powder;
The modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1.5:17;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 4 parts by weight of lanthanum nitrate and 3 parts by weight of europium chloride, adding 8 parts by weight of citric acid, stirring and mixing for 20min, volatilizing a solvent, calcining at 350 ℃ for 1h, washing, and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder;
S3, modification: adding 10 parts by weight of La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S2 into 100 parts by weight of ethanol, adding 1.5 parts by weight of KH560, heating to 45 ℃, stirring and reacting for 3 hours, filtering, washing and drying to prepare modified aerogel;
S4, ring opening: adding 10 parts by weight of the modified aerogel prepared in the step S3 and 4 parts by weight of polyvinyl alcohol 400 into 100 parts by weight of 1, 4-dioxane, adding 0.15 part by weight of boron trifluoride diethyl ether, heating to 95 ℃, and stirring for ring-opening reaction for 1h to obtain polyhydroxy aerogel;
S5, complexing: 100 parts by weight of the polyhydroxy aerogel prepared in the step S4 is added into 200 parts by weight of water, 3 parts by weight of tin nitrate is added, and the mixture is stirred and mixed for 20 minutes, filtered, washed and dried to prepare the catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine.
Comparative example 1
The difference from example 3 is that the modifying liquid is not immersed in step S1.
The method comprises the following steps:
s1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 12 parts by weight of tetraethoxysilane in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, then adding 6 parts by weight of aluminum isopropoxide and 5 parts by weight of zinc acetate, stirring for 15 minutes, dripping ammonia water to adjust the pH value to 8.5, heating to 60 ℃, drying for 1.5 hours to form gel, aging for 2.5 hours, drying, and crushing to obtain SiO 2/Al2O3/ZnO composite aerogel powder.
Comparative example 2
In comparison with example 3, the difference is that aluminum isopropoxide is not added in step S1.
The method comprises the following steps:
S1, preparing SiO 2/ZnO composite aerogel powder: dissolving 12 parts by weight of tetraethoxysilane in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, then adding 11 parts by weight of zinc acetate, stirring for 15 minutes, dropwise adding ammonia water to adjust the pH value to 8.5, heating to 60 ℃ and drying for 1.5 hours to form gel, aging for 2.5 hours, adding the gel into a modified liquid and soaking for 6 hours, then replacing the gel with ethanol, drying and crushing to obtain SiO 2/ZnO composite aerogel powder.
Comparative example 3
The difference from example 3 is that zinc acetate is not added in step S1.
The method comprises the following steps:
S1, preparing SiO 2/Al2O3 composite aerogel powder: dissolving 12 parts by weight of tetraethoxysilane in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, then adding 11 parts by weight of aluminum isopropoxide, stirring for 15 minutes, dropwise adding ammonia water to adjust the pH value to 8.5, heating to 60 ℃ and drying for 1.5 hours to form gel, aging for 2.5 hours, adding the gel into a modified solution and soaking for 6 hours, then replacing the gel with ethanol, drying and crushing to obtain SiO 2/Al2O3 composite aerogel powder.
Comparative example 4
In comparison with example 3, the difference is that aluminum isopropoxide and zinc acetate are not added in step S1.
The method comprises the following steps:
S1, preparing SiO 2 aerogel powder: dissolving 33 parts by weight of tetraethoxysilane in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, dropwise adding ammonia water to adjust the pH value to 8.5, heating to 60 ℃, drying for 1.5 hours to form gel, aging for 2.5 hours, adding the gel into a modified liquid, soaking for 6 hours, then replacing the solvent with ethanol, drying, and crushing to obtain SiO 2 aerogel powder.
Comparative example 5
In comparison with example 3, the difference is that lanthanum nitrate was not added in step S2.
The method comprises the following steps:
S2, preparing Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 7 parts by weight of europium chloride, adding 8 parts by weight of citric acid, stirring and mixing for 20min, volatilizing a solvent, calcining at 350 ℃ for 1h, washing, and drying to prepare Eu doped SiO 2/Al2O3/ZnO composite aerogel powder.
Comparative example 6
In comparison with example 3, the difference is that europium chloride is not added in step S2.
The method comprises the following steps:
S2, preparing La doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 7 parts by weight of lanthanum nitrate, adding 8 parts by weight of citric acid, stirring and mixing for 20min, volatilizing a solvent, calcining at 350 ℃ for 1h, washing, and drying to prepare La-doped SiO 2/Al2O3/ZnO composite aerogel powder.
Comparative example 7
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 12 parts by weight of tetraethoxysilane in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, then adding 6 parts by weight of aluminum isopropoxide and 5 parts by weight of zinc acetate, stirring for 15 minutes, dripping ammonia water to adjust the pH value to 8.5, heating to 60 ℃ and drying for 1.5 hours to form gel, aging for 2.5 hours, adding the gel into a modified solution and soaking for 6 hours, then replacing the gel with ethanol, drying and crushing to prepare SiO 2/Al2O3/ZnO composite aerogel powder;
The modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1.5:17;
S2, modification: adding 10 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of ethanol, adding 1.5 parts by weight of KH560, heating to 45 ℃, stirring and reacting for 3 hours, filtering, washing and drying to prepare modified aerogel;
S3, ring opening: adding 10 parts by weight of the modified aerogel prepared in the step S2 and 4 parts by weight of polyvinyl alcohol 400 into 100 parts by weight of 1, 4-dioxane, adding 0.15 part by weight of boron trifluoride diethyl ether, heating to 95 ℃, and stirring for ring-opening reaction for 1h to obtain polyhydroxy aerogel;
S4, complexing: 100 parts by weight of the polyhydroxy aerogel prepared in the step S3 is added into 200 parts by weight of water, 3 parts by weight of tin nitrate is added, and the mixture is stirred and mixed for 20 minutes, filtered, washed and dried to prepare the catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine.
Comparative example 8
In comparison with example 3, the difference is that steps S3 and S4 are not performed.
The method comprises the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 12 parts by weight of tetraethoxysilane in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, then adding 6 parts by weight of aluminum isopropoxide and 5 parts by weight of zinc acetate, stirring for 15 minutes, dripping ammonia water to adjust the pH value to 8.5, heating to 60 ℃ and drying for 1.5 hours to form gel, aging for 2.5 hours, adding the gel into a modified solution and soaking for 6 hours, then replacing the gel with ethanol, drying and crushing to prepare SiO 2/Al2O3/ZnO composite aerogel powder;
The modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1.5:17;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 4 parts by weight of lanthanum nitrate and 3 parts by weight of europium chloride, adding 8 parts by weight of citric acid, stirring and mixing for 20min, volatilizing a solvent, calcining at 350 ℃ for 1h, washing, and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder;
S3, complexing: adding 100 parts by weight of La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S2 into 200 parts by weight of water, adding 3 parts by weight of tin nitrate, stirring and mixing for 20min, filtering, washing and drying to obtain the catalyst for catalytic synthesis of dimethyl thiotoluene diamine.
Comparative example 9
In comparison with example 3, the difference is that steps S3, S4 and S5 are not performed.
The method comprises the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 12 parts by weight of tetraethoxysilane in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, then adding 6 parts by weight of aluminum isopropoxide and 5 parts by weight of zinc acetate, stirring for 15 minutes, dripping ammonia water to adjust the pH value to 8.5, heating to 60 ℃ and drying for 1.5 hours to form gel, aging for 2.5 hours, adding the gel into a modified solution and soaking for 6 hours, then replacing the gel with ethanol, drying and crushing to prepare SiO 2/Al2O3/ZnO composite aerogel powder;
The modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1.5:17;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 4 parts by weight of lanthanum nitrate and 3 parts by weight of europium chloride, adding 8 parts by weight of citric acid, stirring and mixing for 20min, volatilizing a solvent, calcining at 350 ℃ for 1h, washing, and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder, namely the catalyst for catalytic synthesis of dimethyl thiotoluene diamine.
Comparative example 10
In comparison with example 3, the difference is that steps S2 to S5 are not performed.
The method comprises the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 12 parts by weight of ethyl orthosilicate in 85 parts by weight of ethanol, adding 13 parts by weight of water and 4 parts by weight of acetic acid, heating to 85 ℃, stirring and reacting for 6 hours, then adding 6 parts by weight of aluminum isopropoxide and 5 parts by weight of zinc acetate, stirring for 15 minutes, dropwise adding ammonia water to adjust the pH value to 8.5, heating to 60 ℃ and drying for 1.5 hours to form gel, aging for 2.5 hours, adding the gel into a modified solution and soaking for 6 hours, then replacing the gel with ethanol, drying and crushing to obtain SiO 2/Al2O3/ZnO composite aerogel powder, namely the catalyst for catalyzing and synthesizing dimethyl thiotoluene diamine;
the modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1.5:17.
Test example 1
The specific surface area and the total pore Rong Heping average pore diameter of the catalysts for catalytic synthesis of dimethyl thiotoluenediamine prepared in examples 1 to 3 and comparative examples 1 to 10 were measured by using a 3-FLEX 3500 multi-station high flux gas adsorber.
The results are shown in Table 1.
TABLE 1
。
As can be seen from the above table, the catalysts for catalytic synthesis of dimethyl thiotoluene diamine prepared in examples 1-3 of the present invention have a large specific surface area and a large total pore volume.
Test example 2
The catalysts for catalytic synthesis of dimethyl thiotoluene diamine prepared in examples 1-3 and comparative examples 1-10 were applied to the reaction of preparing dimethyl thiotoluene diamine by catalytic reaction of 2, 4-diaminotoluene and dimethyl disulfide, the addition amount of the catalyst was 0.7wt% of the mass of toluene diamine, the reaction temperature was 120 ℃, the reaction time was 4 hours, and the catalytic performance of each catalyst was analyzed.
The results are shown in Table 2.
TABLE 2
。
As can be seen from the above table, the catalysts for catalytic synthesis of dimethyl thiotoluene diamine prepared in examples 1-3 of the present invention have better catalytic activity and selectivity.
Test example 3
The catalysts for catalytic synthesis of dimethyl thiotoluene diamine prepared in examples 1-3 and comparative examples 1-10 were applied to the reaction of preparing dimethyl thiotoluene diamine by catalytic reaction of 2, 4-diaminotoluene and dimethyl disulfide, the addition amount of the catalyst was 0.7wt% of the mass of toluene diamine, the reaction temperature was 120 ℃, and after continuous catalytic reaction for 200 hours, the catalytic performance of each catalyst was analyzed.
The results are shown in Table 3.
TABLE 3 Table 3
。
As can be seen from the above table, the catalyst for catalytic synthesis of dimethyl thiotoluene diamine prepared in examples 1-3 of the present invention has good catalytic stability, and still has high catalytic activity after long-term catalysis.
Test example 4
The catalysts for catalytic synthesis of dimethylthiotoluenediamine prepared in examples 1 to 3 and comparative examples 1 to 10 of the present invention were subjected to mechanical property test. The samples were tested for compression performance using an electronic compression tester at a compression rate of 1 mm/min.
The results are shown in Table 4.
TABLE 4 Table 4
。
As can be seen from the above table, the catalysts for catalytic synthesis of dimethyl thiotoluene diamine prepared in examples 1-3 of the present invention have good mechanical properties.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. A method for preparing a catalyst for catalytic synthesis of dimethyl thiotoluene diamine, comprising the steps of:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving alkyl orthosilicate in ethanol, adding water and acetic acid, heating and stirring for reacting for a first time period, then adding aluminum alkoxide and zinc acetate, stirring for a second time period, dripping ammonia water for regulating the pH value, drying to form gel, aging, adding the gel into a modified liquid for soaking, then using ethanol for solvent replacement, drying and crushing to obtain SiO 2/Al2O3/ZnO composite aerogel powder;
The modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1-2:15-20;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding the SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into water, adding lanthanum salt and europium salt, adding citric acid, stirring and mixing uniformly, volatilizing a solvent, calcining, washing and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder;
S3, modification: adding the La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S2 into ethanol, adding KH560, heating and stirring for reaction, filtering, washing and drying to obtain modified aerogel;
s4, ring opening: adding the modified aerogel prepared in the step S3 and polyvinyl alcohol into 1, 4-dioxane, adding boron trifluoride diethyl ether, heating, stirring and carrying out ring opening reaction to obtain polyhydroxy aerogel;
S5, complexing: and (3) adding the polyhydroxy aerogel prepared in the step (S4) into water, adding tin salt, stirring and mixing uniformly, filtering, washing and drying to obtain the catalyst for catalytic synthesis of the dimethyl thiotoluene diamine.
2. The preparation method according to claim 1, wherein in the step S1, the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, the aluminum alkoxide is selected from aluminum sec-butoxide or aluminum isopropoxide, the mass ratio of the alkyl orthosilicate, the aluminum alkoxide, the zinc acetate, the ethanol, the water and the acetic acid is 10-15:5-7:4-6:70-100:12-15:3-5, the temperature of the heating and stirring reaction is 80-90 ℃, the first time period is 5-7h, the second time period is 10-20min, the pH value is adjusted to 8-9, the temperature of the gel forming by drying is 55-65 ℃ for 1-2h, the aging time is 2-3h, and the soaking time is 5-7h.
3. The preparation method according to claim 1, wherein in the step S2, the mass ratio of the SiO 2/Al2O3/ZnO composite aerogel powder, lanthanum salt, europium salt and citric acid is 100:3-5:2-4:7-10, the lanthanum salt is at least one selected from lanthanum chloride, lanthanum sulfate and lanthanum nitrate, the europium salt is europium chloride, the calcination temperature is 300-400 ℃, and the calcination time is 0.5-1h.
4. The preparation method of claim 1, wherein in the step S3, the mass ratio of the La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder to KH560 is 10:1-2, the temperature of the heating and stirring reaction is 40-50 ℃ and the time is 2-4h.
5. The preparation method according to claim 1, wherein in the step S4, the mass ratio of the modified aerogel to the polyvinyl alcohol to the boron trifluoride diethyl ether is 10:3-5:0.1-0.2, the polyvinyl alcohol is polyvinyl alcohol 400 or polyvinyl alcohol 1000, the temperature of the heating stirring ring-opening reaction is 90-100 ℃, and the time is 0.5-1h.
6. The preparation method according to claim 1, wherein in the step S5, the mass ratio of the polyhydroxy aerogel to the tin salt is 100:2.5-5, the tin salt is at least one selected from tin chloride, tin sulfate and tin nitrate, and the stirring and mixing time is 15-25min.
7. The preparation method according to claim 1, characterized by comprising the following steps:
S1, preparing SiO 2/Al2O3/ZnO composite aerogel powder: dissolving 10-15 parts by weight of alkyl orthosilicate in 70-100 parts by weight of ethanol, adding 12-15 parts by weight of water and 3-5 parts by weight of acetic acid, heating to 80-90 ℃, stirring for reacting for 5-7 hours, then adding 5-7 parts by weight of aluminum alkoxide and 4-6 parts by weight of zinc acetate, stirring for 10-20 minutes, dripping ammonia water to adjust the pH value to 8-9, heating to 55-65 ℃ for drying for 1-2 hours to form gel, aging for 2-3 hours, adding the gel into a modified liquid, soaking for 5-7 hours, then replacing with ethanol, drying, and crushing to obtain SiO 2/Al2O3/ZnO composite aerogel powder;
The modified liquid is a mixed liquid of trimethylchlorosilane and absolute ethyl alcohol according to the mass ratio of 1-2:15-20;
S2, preparing La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder: adding 100 parts by weight of SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S1 into 100 parts by weight of water, adding 3-5 parts by weight of lanthanum salt and 2-4 parts by weight of europium salt, adding 7-10 parts by weight of citric acid, stirring and mixing uniformly, volatilizing a solvent, calcining at 300-400 ℃ for 0.5-1h, washing and drying to prepare La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder;
S3, modification: adding 10 parts by weight of La/Eu doped SiO 2/Al2O3/ZnO composite aerogel powder prepared in the step S2 into 100 parts by weight of ethanol, adding 1-2 parts by weight of KH560, heating to 40-50 ℃, stirring and reacting for 2-4 hours, filtering, washing and drying to prepare modified aerogel;
S4, ring opening: adding 10 parts by weight of the modified aerogel prepared in the step S3 and 3-5 parts by weight of polyvinyl alcohol into 100 parts by weight of 1, 4-dioxane, adding 0.1-0.2 part by weight of boron trifluoride diethyl ether, heating to 90-100 ℃, stirring and carrying out ring opening reaction for 0.5-1h to obtain polyhydroxy aerogel;
S5, complexing: adding 100 parts by weight of the polyhydroxy aerogel prepared in the step S4 into 200 parts by weight of water, adding 2.5-5 parts by weight of tin salt, stirring and mixing for 15-25min, filtering, washing and drying to obtain the catalyst for catalyzing and synthesizing the dimethyl thiotoluene diamine.
8. A catalyst for catalytic synthesis of dimethylthiotoluenediamine produced by the production process according to any one of claims 1 to 7.
9. Use of the catalyst of claim 8 for the catalytic synthesis of dimethyl thiotoluene diamine.
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| CN116393053A (en) * | 2023-06-02 | 2023-07-07 | 江苏珈云新材料有限公司 | Modified nano SiO 2 Aerogel and preparation method thereof |
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| CN104722290A (en) * | 2015-01-30 | 2015-06-24 | 南京航空航天大学 | Modifier doped inorganic compound aerogel catalyst and preparation method thereof |
| CN115418144A (en) * | 2022-08-19 | 2022-12-02 | 复旦大学 | Antifogging coating material of polyvinyl alcohol with ultra-low alcoholysis degree and preparation method thereof |
| CN116617954A (en) * | 2023-05-08 | 2023-08-22 | 东营海瑞宝新材料有限公司 | Production device and production method of dimethyl thiotoluene diamine |
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