CN115646544A - Supported platinum catalyst, preparation method and preparation method of Gemini type quaternary ammonium salt - Google Patents
Supported platinum catalyst, preparation method and preparation method of Gemini type quaternary ammonium salt Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 33
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003607 modifier Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 55
- 238000005956 quaternization reaction Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 29
- 238000005576 amination reaction Methods 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 24
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 22
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 17
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 16
- 229920002545 silicone oil Polymers 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 13
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 9
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical compound CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229960003194 meglumine Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000005703 Trimethylamine hydrochloride Substances 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940073608 benzyl chloride Drugs 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 19
- 239000002979 fabric softener Substances 0.000 abstract description 18
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 13
- 238000004383 yellowing Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 52
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000004593 Epoxy Substances 0.000 description 12
- FLLFKFMTRYRALL-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxy-n-methylhexanamide Chemical compound CNC(=O)C(O)C(O)C(O)C(O)CO FLLFKFMTRYRALL-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000011949 solid catalyst Substances 0.000 description 8
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- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- ARBABAXCNWMWMS-UHFFFAOYSA-N 6-hydroxy-n-methylhexanamide Chemical compound CNC(=O)CCCCCO ARBABAXCNWMWMS-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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Abstract
The invention discloses a supported platinum catalyst, a preparation method and a preparation method of a Gemini quaternary ammonium salt, wherein the catalyst comprises graphene oxide, platinum atoms and a modifier connected between the platinum atoms and the graphene oxide; the invention belongs to the field of fabric modifiers, and discloses a supported platinum catalyst which is high in conversion rate, high in yield of a beta-addition product of a prepared fabric softener and small in yellowing property of the prepared fabric softener. Meanwhile, the invention also provides a preparation method of the fabric softener, and the fabric softener prepared by the method can achieve the purpose of synergistically improving the whiteness, flexibility, hydrophilicity and antibacterial property of the fabric.
Description
Technical Field
The invention relates to the field of fabric modifiers, in particular to a supported platinum catalyst, a preparation method and a preparation method of a Gemini type quaternary ammonium salt.
Background
Silicones are widely used as fabric softeners, a class of chemicals that change the static and dynamic coefficients of friction of fibers. When the static friction coefficient is changed, the hand feeling is smooth and easy to move on the fiber or fabric; when the coefficient of dynamic friction is changed, the fine structures between the fibers tend to move relative to each other, that is, the fibers or the fabric tend to be deformed. The combined feel of the two is soft. The softening agent is classified into four types, i.e., a cationic type, a nonionic type, an anionic type, and an amphoteric quaternary ammonium salt type, in terms of ionic properties.
In the prior art, modification research aiming at a fabric softener mainly focuses on the aspect of structural improvement of an additional group, for example, an invention patent ZL201310746590.8 proposed by Shanghai Kai chemical Co., ltd in 2013 of the applicant adopts N, N-dimethyl-N' -glycolyl-1,3-propane diamine as a modification group to improve the effects of softness, whiteness, antibacterial property and the like.
For example, the fabric softener prepared based on the quaternization reaction of the amino-terminated polyether, which is proposed by macrographic assistant company Limited on the Qing Shang market of the applicant in 2016, has certain contribution in aspects of fabric whiteness, softness and the like.
However, the applicant believes that in addition to the above-described preference based on substituent groups to improve the performance of fabric softeners, the purity of the fabric softener, thoroughness during the addition reaction, etc. remain to be neglected.
A platinum catalyst has been proposed as a catalyst for a fabric softener, for example, an invention patent application CN201810665395.5 proposed by the applicant, new sea hong chemical limited in north of huh in 2018 discloses a preparation method of a fabric softener, which comprises the following steps: s1, obtaining a hydrogen-terminated polysiloxane intermediate by using D4 and an HMM end capping agent under the action of an acid catalyst; s2, reacting the hydrogen-terminated polysiloxane intermediate obtained in the step S1 with vinylene carbonate under the action of a platinum catalyst to obtain a diepoxy terminated polysiloxane intermediate; and S3, mixing the diepoxy terminated polysiloxane intermediate obtained in the step S2 with polyetheramine to prepare a light yellow transparent liquid. The catalyst is Karstedt catalyst which is prepared by chloroplatinic acid/salt under the heating action in the presence of ethanol and sodium bicarbonate.
As a catalyst of the same type, a catalyst similar to the Karstedt catalyst may also be selected as the graphene-supported platinum catalyst.
Reference may be made to patent application ZL201110053701.8 by the university of south-river science and technology in 2011, which proposes a dendritic supported platinum catalyst. Referring to this technology, several simplified supported platinum catalysts were investigated during the course of the study, and not all supported platinum catalysts were found to be able to meet our expectations.
Based on the above-mentioned realistic conditions, the technical problem that this application will solve lies in: 1. the catalyst is provided to solve the problems that in the prior art, the number of byproducts of the hydrosilylation reaction is large, and the product turns yellow in the catalysis process of the fabric softener; 2. based on the catalyst, a modifier suitable for the catalyst is further provided to solve the problem that the whiteness, flexibility, hydrophilicity and antibacterial property of the fabric after the fabric softener is used for treating the fabric can not be synergistically improved.
Disclosure of Invention
The invention aims to provide a supported platinum catalyst and a preparation method thereof, the supported platinum catalyst has high conversion rate, the content of the prepared fabric softener beta addition product is high, and the prepared fabric softener Huang Biandi is obtained.
Meanwhile, the invention also provides a supported platinum catalyst, which comprises graphene oxide, platinum atoms and a modifier connected between the platinum atoms and the graphene oxide;
the modifier is tetraethylenepentamine or pentaethylene hexamine.
In the above-mentioned supported platinum catalyst, the modifier is tetraethylenepentamine.
Meanwhile, the invention also discloses a preparation method of the supported platinum catalyst, which comprises the following steps: dispersing graphene oxide in an organic solvent, adding a modifier to enable the modifier to be connected to the surface of the graphene oxide, and drying to obtain powder which is marked as GO-PEPA;
mixing GO-PEPA and H 2 PtCl 6 ·6H 2 And mixing the O in absolute ethyl alcohol, reacting, filtering, and drying to obtain the supported platinum catalyst, which is recorded as GO-TEPA-Pt.
In the above preparation method of the supported platinum catalyst, the method specifically comprises:
ultrasonically dispersing 7.0g of graphene oxide in 7000ml of N-methylpyrrolidone solvent, continuously adding 7.0 ml tetraethylenepentamine or pentaethylenehexamine, continuously ultrasonically stirring for 15min, slowly heating to 110 ℃, and reacting for 24 h; performing suction filtration, and washing with methanol, water and acetone in sequence; vacuum drying the product at 80 ℃ for 12 h, and grinding to obtain powder which is marked as GO-PEPA;
dispersing 2g of GO-PEPA powder in 120 ml absolute ethyl alcohol, and sequentially adding 0.032 g of NaHCO 3 And 0.05 g of H 2 PtCl 6 ·6H 2 O, stirring the mixture at 40 ℃ for 24 h; after the reaction is finished, carrying out suction filtration, washing for 6 times by using absolute ethyl alcohol, and carrying out vacuum drying on the product at 70 ℃ for 12 h; the product is marked as GO-TEPA-Pt.
Finally, the invention also discloses a preparation method of the Gemini type quaternary ammonium salt, which comprises the following steps:
step 1: hydrosilylation, adding tetramethyldisiloxane into allyl glycidyl ether in the presence of the catalyst, wherein the molar ratio of the allyl glycidyl ether to the tetramethyldisiloxane is 1:2-2.5, and reacting to obtain EDH;
step 2: chain extension, namely reacting D4 and EDH in the presence of tetramethylammonium hydroxide to obtain epoxy-terminated modified silicone oil; the mass ratio of D4 to EDH is as follows: (37.9-60.2): 1;
and step 3: amination, namely reacting the epoxy-terminated modified silicone oil with meglumine to obtain an amination product; the mol ratio of the epoxy-terminated modified silicone oil to the meglumine is as follows: 1: (0.8-1.3);
and 4, step 4: quaternization, namely reacting the amination product with a quaternization agent to obtain Gemini type quaternary ammonium salt; the mol ratio of amination products to quaternizing agents is 1.
In the above method for preparing gemini quaternary ammonium salts, in step 1, the amount of the catalyst is 3-15 ppm based on the total weight of allyl glycidyl ether and tetramethyldisiloxane; in step 2, the tetramethylammonium hydroxide is equivalent to 0.01-0.03 wt percent of the total weight of D4 and EDH.
In the preparation method of the Gemini type quaternary ammonium salt, in the step 1, the reaction temperature is 80-100 ℃, and the reaction time is 2-4h; in the step 1, after the reaction is finished, heating and decompressing to remove low-boiling-point substances to obtain colorless transparent liquid, namely the beta-addition product.
In the preparation method of the Gemini quaternary ammonium salt, in the step 2, the reaction temperature is 90-110 ℃, and the reaction is 8-12 h.
In the preparation method of the Gemini type quaternary ammonium salt, the reaction temperature of the step 3 and the step 4 is 75-85 ℃; the reaction time of the step 3 is 6-10h; the reaction time of the step 4 is 3-5h.
In the preparation method of the Gemini type quaternary ammonium salt, the molecular weight of the Gemini type quaternary ammonium salt is 4000-13000, and the quaternizing agent in the step 4 is one of dimethyl sulfate, benzyl chloride, 3-chloropropyltrimethoxysilane and trimethylamine hydrochloride.
The reaction process of the above reaction formula is as follows:
compared with the prior art, the invention has the beneficial effects that:
the supported platinum catalyst has high conversion rate, the EDH yield of the prepared fabric softener is high, and the prepared fabric softener Huang Biandi is obtained.
After the fabric softener prepared by the method disclosed by the invention is used for treating the fabric, the aim of synergistically improving the whiteness, flexibility, hydrophilicity and antibacterial property of the fabric can be fulfilled.
Drawings
FIG. 1 is a Fourier transform infrared spectrum of example 3 of the present invention;
FIG. 2 is a NMR spectrum of example 3 of the present invention;
FIG. 3 is the reaction equation of EDH of example 3 of the present invention;
FIG. 4 is a gas chromatogram of chloroplatinic acid and GO-TEPA-Pt catalyzed EDH of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Ultrasonically dispersing 7.0g of graphite oxide in 7000ml of N-methylpyrrolidone solvent, continuously adding 7.0 ml tetraethylenepentamine, continuously ultrasonically stirring for 15min, slowly heating to 110 ℃, and reacting 24 h. Filtering, washing with methanol, water and acetone in sequence. The product was vacuum dried at 80 ℃ for 12 h and ground to give a powder, designated GO-TEPA.
2g of GO-TEPA powder is dispersed in 120 ml absolute ethyl alcohol, and 0.032 g of NaHCO is added in sequence 3 And 0.05 g of H 2 PtCl 6 ·6H 2 O, the mixture was stirred at 40 ℃ for 24 h. After the reaction, the reaction solution is filtered, washed with absolute ethyl alcohol for 6 times, and the product is dried in vacuum at 70 ℃ for 12 h. The product was noted as GO-TEPA-Pt catalyst.
Example 2
Ultrasonically dispersing 7.0g of graphite oxide in 7000ml of N-methylpyrrolidone solvent, continuously adding 7.0 ml pentaethylene hexamine, continuously ultrasonically treating for 15min, stirring, slowly heating to 110 ℃, and reacting 24 h. Filtering, washing with methanol, water and acetone in sequence. The product was vacuum dried at 80 ℃ for 12 h and ground to give a powder, designated GO-PEHA.
Dispersing 2g of GO-PEHA powder in 120 ml absolute ethyl alcohol, and sequentially adding 0.032 g of NaHCO 3 And 0.05 g of H 2 PtCl 6 6H2O, the mixture is stirred at 40 ℃ for 24H. After the reaction, the reaction solution is filtered, washed with absolute ethyl alcohol for 6 times, and the product is dried in vacuum at 70 ℃ for 12 h. The product is marked as GO-PEHA-Pt catalyst.
Example 3
Step 1: hydrosilylation, 114g of allyl glycidyl ether and GO-TEPA-Pt catalyst are added, and N is introduced 2 Heating to 50 ℃, dropwise adding 326.6g tetramethyldisiloxane within 1h (molar ratio 1. And (3) filtering to separate out the solid catalyst, heating the colorless transparent liquid to 120 ℃, decompressing (-0.09 to 0.1MPa) for 1h, and removing low-boiling-point substances to obtain the colorless transparent liquid, namely the epoxy double-end-socket EDH.
Step 2: chain extension, adding 1000g D4 and 114.5g EDH, solid tetramethyl ammonium hydroxide (0.02 wt%) into a four-neck flask, heating to 90-110 ℃, reacting for 10h, then heating to 145-150 ℃, and 0.5h decomposing catalyst. Then decompressing to 0.09 to 0.1MPa for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And step 3: amination, adding 1000g of chain extension product, 72.97g N-methyl-2,3,4,5,6-pentahydroxyhexanamide (molar ratio 1.2) and 715.32g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 74.28g of quaternizing agent (the molar ratio is 1:1) into the flask obtained in the step 3, heating to 80 ℃, reacting for 3 hours, and carrying out quaternization reaction to obtain Gemini type quaternary ammonium salt.
FIG. 1 is the IR infrared spectra of EDH and product BPSQA; in fig. 1: the abscissa is the wavelength; the ordinate is the transmittance; HMM is tetramethyldisiloxane, AGE is allyl glycidyl ether, EDH is epoxy bis-end-cap, ETSO is terminal epoxy silicone oil, PTSO is the amination product, BPSQA is a gemini quaternary ammonium salt. It was found that the hydroxyl and quaternary ammonium salt group characteristic groups were successfully introduced in the final product. Wherein, 3500 cm -1 Characteristic absorption peak of-OH, 1392cm -1 is-NH 4 + 1004 cm -1 The C-N characteristic absorption peak of the quaternary ammonium salt is that the C-N stretching vibration frequency is similar to the C-O stretching vibration frequency, but the C-N absorption band is weaker than the C-O absorption band. Taken together, it was preliminary shown that the synthesis gave the expected target product BPSQA.
FIG. 2 is a drawing of EDH and product BPSQA 1 H NMR nuclear magnetic resonance spectrum;
addition reaction, chemical shift of HMM at 4.4ppm Si-H disappeared completely. H and e on the epoxy group respectively correspond to chemical shifts at 2.5ppm, 2.7ppm and 3.1ppm in a nuclear magnetic spectrum, and mainly come from the fact that the existence of the epoxy group causes the space position to be reduced, and two H positions are different to generate splitting. -CH bound to an epoxy group 2 Split into two peaks, j and h, exactly with-CH at f for the same reason 2 The nuclear magnetic resonance peaks of (a) form an overlap.
Quaternization reaction, δ (ppm): 0.00 (a, si-CH) 3 ），0.44（b，Si-CH 2 ）），1.14（c，-OCH 2 CHCH 3 -），1.53（d，Si-CH 2 CH 2 -）），2.71（e,-CH 2 -NH- -NH-CHCH 3 ），3.35（f，-OCH 2 CHCH 3- ），3.57（g，-O-CH 2 CH 2 -), 3.96 (h, -OH). The peak intensities and integrated areas of peaks a, c and g are maximal, respectively, and are represented by PTSO (Si-CH) 3 ) The nuclear magnetic resonance peak of the corresponding proton shows the introduction of the polysiloxane chain segment in the molecule; the nuclear magnetic peak of the proton in the corresponding-OH at the h position indicates that the ring opening reaction of the ETSO has occurred; because the content of amino in the molecule is less, no obvious resonance peak exists in a nuclear magnetic spectrum.
Example 4
Step 1: hydrosilylation, 114g of allyl glycidyl ether and GO-PEHA-Pt catalyst are added, and N is introduced 2 Heating to 50 ℃, dropwise adding 326.6g tetramethyldisiloxane within 1h (molar ratio 1. And filtering to separate out the solid catalyst, heating the colorless transparent liquid to 120 ℃, decompressing to-0.09 to 0.1MPa for 1h, and removing low-boiling-point substances to obtain the colorless transparent liquid, namely the epoxy double-end-socket EDH.
Step 2: chain extension, adding 1000g of D4 and 68.9g of EDH, solid tetramethyl ammonium hydroxide (0.02 wt%) into a four-neck flask, heating to 90-110 ℃, reacting for 10h, then heating to 145-150 ℃, and heating to 0.5h to decompose the catalyst. Then decompressing (-0.09 to-0.1 MPa) for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And step 3: amination, adding 1000g of chain extension product, 44.96g N-methyl-2,3,4,5,6-pentahydroxyhexanamide (molar ratio 1.2) and 696.64g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 45.81g of quaternization reagent chloropropyltrimethoxysilane (the molar ratio is 1:1) into the flask obtained in the step 3, heating to 80 ℃, reacting for 3 hours, and carrying out quaternization reaction to obtain the Gemini type quaternary ammonium salt.
Example 5
Step 1: hydrosilylation, 114g of allyl glycidyl ether, GO-TEPA-Pt catalyst and N 2 Heating to 50 ℃, dropwise adding 284g of tetramethyldisiloxane, completing dropwise addition within 1h (the molar ratio is 1:2), heating to 90 ℃, and keeping the temperature for 3h. And filtering to separate out the solid catalyst, heating the colorless transparent liquid to 120 ℃, decompressing to-0.09 to 0.1MPa for 1h, and removing low-boiling-point substances to obtain the colorless transparent liquid, namely the epoxy double-end-socket EDH.
Step 2: chain extension, namely adding 1000g of D4 and 68.9g of EDH (the mass ratio is 100. Then decompressing to 0.09 to 0.1MPa for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And step 3: amination, adding 1000g of chain extension product, 47.44g N-methyl-2,3,4,5,6-pentahydroxyhexanamide (molar ratio 1.8) and 711.63g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 54.92g of quaternization reagent chloropropyltrimethoxysilane (molar ratio is 1.
Example 6
Step 1: hydrosilylation, 114g of allyl glycidyl ether and GO-TEPA-Pt-1 catalyst are added, and N is introduced 2 Heating to 50 ℃, dropwise adding 355g of tetramethyldisiloxane, completing dropwise adding within 1h (molar ratio is 1. And (3) filtering to separate out the solid catalyst, heating the colorless transparent liquid to 120 ℃, decompressing (-0.09 to 0.1MPa) for 1h, and removing low-boiling-point substances to obtain the colorless transparent liquid, namely the epoxy double-end-socket EDH.
Step 2: chain extension, adding 1000g D4 and 49.1g EDH, solid tetramethyl ammonium hydroxide (0.02 wt%) into a four-neck flask, heating to 90-110 ℃, reacting for 10h, then heating to 145-150 ℃, and 0.5h decomposing catalyst. Then decompressing to 0.09 to 0.1MPa for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And step 3: amination, adding 1000g of chain extension product, 40.61g N-methyl-2,3,4,5,6-pentahydroxyhexanamide (molar ratio 1.5) and 693.74g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 49.6g of quaternization reagent chloropropyltrimethoxysilane (molar ratio is 1: 1.2) into the flask obtained in the step 3, heating to 80 ℃, reacting for 3h, and carrying out quaternization reaction to obtain Gemini type quaternary ammonium salt.
Example 7
Step 1: hydrosilylation, 114g of allyl glycidyl ether and GO-TEPA-Pt catalyst are added, and N is introduced 2 Heating to 50 ℃, dripping 312.4g of tetramethyldisiloxane, finishing dripping within 1h (molar ratio is 1. And filtering to separate out the solid catalyst, heating the colorless transparent liquid to 120 ℃, decompressing (-0.09 to 0.1MPa) for 1h, and removing low-boiling-point substances to obtain the colorless transparent liquid, namely the epoxy double-end-socket EDH.
Step 2: chain extension, namely adding 1000g of D4 and 34.4g of a beta-addition reaction product (the mass ratio is 100. Then decompressing to 0.09 to 0.1MPa for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And step 3: amination, adding 1000g of chain extension product, 28.71g N-methyl-2,3,4,5,6-pentahydroxyhexanamide (molar ratio 1.5) and 685.82g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 32.15g of quaternization reagent chloropropyltrimethoxysilane (molar ratio is 1: 1.1) into the flask obtained in the step 3, heating to 80 ℃, reacting for 3h, and carrying out quaternization reaction to obtain Gemini type quaternary ammonium salt.
Example 8
Step 1: hydrosilylation, 114g of allyl glycidyl ether, GO-TEPA-Pt catalyst and N 2 Heating to 50 ℃, dropwise adding 326.6g tetramethyldisiloxane within 1h (molar ratio 1. And filtering to separate out the solid catalyst, heating the colorless transparent liquid to 120 ℃, decompressing (-0.09 to 0.1MPa) for 1h, and removing low-boiling-point substances to obtain the colorless transparent liquid, namely the epoxy double-end-socket EDH.
Step 2: chain extension, adding 1000g D4 and 28.6g beta-addition reaction product, solid tetramethyl ammonium hydroxide (0.02 wt%) into a four-neck flask, heating to 90-110 ℃, reacting for 10h, then heating to 145-150 ℃, and decomposing catalyst for 0.5 h. Then decompressing to 0.09 to 0.1MPa for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And step 3: amination, adding 1000g of chain extension product, 19.18g N-methyl-2,3,4,5,6-pentahydroxyhexanamide (molar ratio 1.2) and 679.45g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 23.43g of quaternization reagent chloropropyltrimethoxysilane (molar ratio is 1: 1.1) into the flask in the step 3, heating to 80 ℃, reacting for 3h, and carrying out quaternization reaction to obtain Gemini type quaternary ammonium salt.
Comparative example 1
Ultrasonically dispersing 7.0g of graphite oxide in 7000ml of N-methylpyrrolidone solvent, continuously adding 7.0 ml of 3-aminopropyltrimethoxysilane, continuously ultrasonically treating for 15min, stirring, slowly heating to 110 ℃, and reacting 24 h. Filtering, washing with methanol, water and acetone in sequence. The product was vacuum dried at 80 ℃ for 12 h and ground to give a powder designated GO-151.
Dispersing 2g of GO-PEPA powder in 120 ml absolute ethyl alcohol, and sequentially adding 0.032 g of NaHCO 3 And 0.05 g of H 2 PtCl 6 6H2O, the mixture is stirred at 40 ℃ for 24H. After the reaction, the reaction solution is filtered, washed with absolute ethyl alcohol for 6 times, and the product is dried in vacuum at 70 ℃ for 12 h. The product was noted as GO-151-Pt catalyst.
Comparative example 2
Step 1: hydrosilylation, 114g of allyl glycidyl ether and GO-151-Pt catalyst are added, and N is introduced 2 Heating to 50 ℃, dropwise adding 326.6g tetramethyldisiloxane within 1h (molar ratio 1. And filtering to separate out the solid catalyst, heating the colorless transparent liquid to 120 ℃, decompressing to-0.09 to 0.1MPa for 1h, and removing low-boiling-point substances to obtain the colorless transparent liquid, namely the epoxy double-end-socket EDH.
And 2, step: chain extension, 1000g D4 and 68.9g EDH, solid tetramethyl ammonium hydroxide (0.02 wt%) are added into a four-neck flask, the temperature is raised to 90-110 ℃,10 h is reacted, then the temperature is raised to 145-150 ℃, and 0.5h decomposition catalyst. Then decompressing to 0.09 to 0.1MPa for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And 3, step 3: amination, adding 1000g of chain extension product, 44.96g N-methyl-2,3,4,5,6-pentahydroxyhexanamide (molar ratio 1.2) and 696.64g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 50.39g of quaternization reagent chloropropyltrimethoxysilane (molar ratio is 1: 1.1) into the flask obtained in the step 3, heating to 80 ℃, reacting for 3h, and carrying out quaternization reaction to obtain Gemini type quaternary ammonium salt.
Comparative example 3
Step 1: hydrosilylation, 114g of allyl glycidyl ether, speier catalyst and N 2 Heating to 50 ℃, dropwise adding 326.6g tetramethyldisiloxane within 1h (molar ratio 1. Heating to 120 ℃, decompressing (-0.09 to 0.1MPa) for 1h, and removing low-boiling-point substances to obtain colorless transparent liquid, namely the epoxy double-end-socket EDH.
And 2, step: chain extension, 1000g D4 and 37.8g EDH, solid tetramethyl ammonium hydroxide (0.02 wt%) are added into a four-neck flask, the temperature is raised to 90-110 ℃,10 h is reacted, then the temperature is raised to 145-150 ℃, and 0.5h decomposition catalyst. Then decompressing to 0.09 to 0.1MPa for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And step 3: amination, adding 1000g of chain extension product, 25.72g N-methyl-2,3,4,5,6-pentahydroxyhexanamide (molar ratio 1.2) and 22.97g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 25.72g of quaternization reagent chloropropyltrimethoxysilane (molar ratio is 1.1).
Comparative example 4
Step 1: hydrosilylation, 114g of allyl glycidyl ether and GO-151-Pt catalyst are added, and N is introduced 2 Heating to 50 ℃, dropwise adding 326.6g tetramethyldisiloxane within 1h (molar ratio 1. Is filteredSeparating out the solid catalyst, heating the colorless transparent liquid to 120 ℃, decompressing to-0.09 to 0.1MPa for 1h, and removing low-boiling-point substances to obtain the colorless transparent liquid, namely the epoxy double-end-socket EDH.
Step 2: chain extension, adding 1000g of D4 and 68.9g of EDH, solid tetramethyl ammonium hydroxide (0.02 wt%) into a four-neck flask, heating to 90-110 ℃, reacting for 10h, then heating to 145-150 ℃, and heating to 0.5h to decompose the catalyst. And then decompressing for-0.09 to-0.1MPa for 0.5h, and removing low-boiling-point substances to obtain colorless transparent viscous liquid, namely the epoxy-terminated modified silicone oil.
And 3, step 3: amination, adding 1000g of chain extension product, 44.96g N-methyl-6-hydroxyhexanamide (molar ratio 1: 1.2) and 696.64g of isopropanol into a four-neck flask, heating to 80 ℃, and reacting for 8 hours to obtain an amination product;
and 4, step 4: quaternization, namely adding 45.81g of quaternization reagent (the molar ratio is 1:1) into the flask obtained in the step 3, heating to 80 ℃, reacting for 3 hours, and carrying out quaternization reaction to obtain the gemini quaternary ammonium salt.
Through the above experiment, it can be found that: the GO-TEPA-Pt catalyst is adopted to catalyze the hydrosilylation reaction of AGE and HMM silicon to prepare the epoxy double-end-socket EDH, and the reaction is mainly beta-addition due to the steric hindrance effect of the group (figure 3). In order to follow the contents of 2 addition products during the reaction, the crude product was analyzed for the ratio of α -addition product and β -addition product by Gas Chromatography (GC) after the reaction, and the results are shown in fig. 4. Products at the retention time of 14.715 min and 15.385 min are respectively an alpha-addition product and a beta-addition product, the content of the GO-TEPA-Pt catalyst corresponding to the beta-addition product reaches 99.55% (b in fig. 4), the content of the Speier catalyst corresponding to the beta-addition product reaches 95.39% (a in fig. 4), and it can be seen that the preparation method provided by the invention remarkably improves the yield of the beta-addition product because a large number of oxygen-containing groups such as-COOH, -CHO and-OH are arranged on the surface of graphene oxide, and when GO directly supports Pt particles (i.e. GO-Pt catalyst), pt atoms are easy to agglomerate to form Pt particles with larger particles; when the carrier GO is loaded with Pt particles after being modified by amino, a part of amino in TEPA is connected with-OH on the surface of graphene oxide, and Pt in chloroplatinic acid precursor 4+ Is reduced to Pt 0 After atom, another part of amino groups in TEPA is firmly fixedThe coordination is formed between the Pt and the ground, so that Pt particles are firmly anchored near N, the agglomeration of Pt particles is weakened, the particle size is reduced, the Pt dispersity is improved, the Pt particles are uniformly distributed on the surface of GO-TEPA in the form of Pt atom clusters, the active surface area of the Pt particles is increased, the catalytic activity is improved, and the reaction is more prone to beta-addition.
The detection method comprises the following steps:
1. whiteness degree
And (3) whiteness testing: a WSB-3A type whiteness meter is adopted for testing.
2. Flexibility
A panel of industry experts scored the finished fabric by touch. Five people respectively score and rank the fabrics finished by different gemini quaternary ammonium salts, the higher the ranking, the better the softness of the fabrics is represented, and then the average number is taken as the final score.
3. Hydrophilicity
The hydrophilicity test uses a standard dropper (a drop of water is dropped from a distance from the height of the fabric to the surface of the fabric spreading horizontally, and a stopwatch is used to record the time it takes for the fabric to absorb the drop (i.e., the water spreads completely across the surface of the fabric).
And (3) detection results:
(1) Whiteness, softness, hydrophilicity
Table 1 results of whiteness, softness and hydrophilicity tests on fabrics
The following conclusions can be drawn from the above tests:
1. the adoption of tetraethylenepentamine and pentaethylenehexamine as the modifier of the catalyst has advantages respectively; in the aspect of whiteness, the tetraethylenepentamine has better performance as a modifier of the catalyst; pentaethylenehexamine performs better in terms of antibacterial properties. But in any event, it is superior to the use of tetramethyldisiloxane as the catalyst-supported silane modifier.
2. The antibacterial performance of the N-methyl-6-hydroxyhexanamide is inferior to that of N-methyl-2,3,4,5,6-pentahydroxyhexanamide.
Overall, through many experimental analyses, it can be deduced that:
the antibacterial mechanism is as follows: quaternary ammonium salts are positively charged and can adsorb to the surface of microorganisms that are generally negatively charged; the product is endowed with hydrolyzable organosilicon by the quaternizing agent, mild network crosslinking can be generated after the organosilicon is hydrolyzed, the density of positive charges in molecules is high, the bactericidal groups are dense, the bactericidal agent can effectively diffuse and penetrate cell walls and is combined with cell membranes with negative charges, and the bactericidal capability is enhanced.
The mechanism of antimicrobial diversity is: the catalyst is selected, the polyamine modifier has more obvious advantages than a silane modifier, the amine group in the middle of the polyamine is connected with graphene oxide, and the amines at two ends of the polyamine are connected with platinum; in particular, the use of tetraethylenepentamine, which is more symmetrical when immobilizing platinum, allows more β -addition products to be produced, which is beneficial for the improvement of whiteness, and the β -addition products do not contribute significantly to the antibacterial properties, and as a result, pentaethylenehexamine performs better.
The ammoniation reagent has obvious influence on antibacterial property and whiteness, and particularly, the more hydroxyl groups of the ammoniation reagent, the better the antibacterial property; in the aspect of whiteness, polyhydroxy can improve the affinity performance of the surface of the fabric, so that whiteness improvement and hydrophilicity contribute to certain degree. In the aspect of antibacterial property, the antibacterial agent can be effectively combined with amino and hydroxyl on the surface of bacteria, and the binding capacity to the bacteria is improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A supported platinum catalyst characterized by: the catalyst comprises graphene oxide, platinum atoms and a modifier connected between the platinum atoms and the graphene oxide;
the modifier is Tetraethylenepentamine (TEPA) or Pentaethylenehexamine (PEHA) in polyethylene polyamine (PEPA).
2. The supported platinum catalyst of claim 1, wherein: the modifier is tetraethylenepentamine.
3. A preparation method of a supported platinum catalyst is characterized by comprising the following steps: the method comprises the following steps: dispersing graphene oxide in an organic solvent, adding a modifier to enable the modifier to be connected to the surface of the graphene oxide, and drying to obtain powder which is marked as GO-PEPA;
GO-PEPA, H 2 PtCl 6 ·6H 2 And mixing the O in absolute ethyl alcohol, reacting, filtering, and drying to obtain the supported platinum catalyst, which is recorded as GO-PEPA-Pt.
4. The method for preparing a supported platinum catalyst according to claim 3, wherein: the method specifically comprises the following steps:
ultrasonically dispersing 7.0g of graphene oxide in 7000ml of N-methylpyrrolidone solvent, continuously adding 7.0 ml tetraethylenepentamine or pentaethylenehexamine, continuously ultrasonically stirring for 15min, slowly heating to 110 ℃, and reacting for 24 h; performing suction filtration, and washing with methanol, water and acetone in sequence; vacuum drying the product at 80 ℃ for 12 h, and grinding to obtain powder which is marked as GO-PEPA;
dispersing 2g of GO-PEPA powder in 120 ml absolute ethyl alcohol, and sequentially adding 0.032 g of NaHCO 3 And 0.05 g of H 2 PtCl 6 ·6H 2 O, stirring the mixture at 40 ℃ for 24 h; after the reaction is finished, carrying out suction filtration, washing for 6 times by using absolute ethyl alcohol, and carrying out vacuum drying on the product at 70 ℃ for 12 h; the product is marked as GO-PEPA-Pt.
5. The preparation method of the Gemini type quaternary ammonium salt is characterized by comprising the following steps:
step 1: hydrosilylation, adding tetramethyl disiloxane into allyl glycidyl ether in the presence of the catalyst of claim 1 or 2, wherein the molar ratio of the allyl glycidyl ether to the tetramethyl disiloxane is 1:2-2.5, and reacting to obtain EDH;
step 2: chain extension, namely reacting D4 and EDH in the presence of tetramethylammonium hydroxide to obtain epoxy-terminated modified silicone oil; the mass ratio of D4 to EDH is as follows: 37.9-60.2;
and step 3: amination, namely reacting the epoxy-terminated modified silicone oil with meglumine to obtain an amination product; the mol ratio of the epoxy-terminated modified silicone oil to the meglumine is as follows: 1:0.8 to 1.3;
and 4, step 4: quaternization, namely reacting the amination product with a quaternization reagent to obtain Gemini type quaternary ammonium salt; the mol ratio of amination products to quaternizing agents is 1.
6. The method for preparing a gemini quaternary ammonium salt according to claim 5, wherein in the step 1, the amount of the catalyst is 3 to 15 ppm based on the total weight of allyl glycidyl ether and tetramethyldisiloxane; in step 2, the tetramethylammonium hydroxide is equivalent to 0.01-0.03 wt percent of the total weight of D4 and EDH.
7. The method for preparing a Gemini type quaternary ammonium salt according to claim 5, wherein in the step 1, the reaction temperature is 80-100 ℃, and the reaction time is 2-4h; in the step 1, after the reaction is finished, heating and decompressing to remove low-boiling-point substances to obtain colorless transparent liquid, namely EDH.
8. The preparation method of Gemini quaternary ammonium salt according to claim 5, wherein the reaction temperature in step 2 is 90-110 ℃ and 8-12 h is reacted.
9. The method for preparing a Gemini quaternary ammonium salt according to claim 5, wherein the reaction temperature of the step 3 and the step 4 is 75-85 ℃; the reaction time of the step 3 is 6-10h; the reaction time of the step 4 is 3-5h.
10. The method for preparing a Gemini type quaternary ammonium salt according to claim 5, wherein the molecular weight of the Gemini type quaternary ammonium salt is 4000-13000, and the quaternizing agent in step 4 is one of dimethyl sulfate, benzyl chloride, 3-chloropropyltrimethoxysilane and trimethylamine hydrochloride.
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| CN116273166A (en) * | 2023-03-21 | 2023-06-23 | 广东工业大学 | Pt-transition metal bimetal doped CTF-1 composite material and preparation method and application thereof |
| CN116713033A (en) * | 2022-11-21 | 2023-09-08 | 广东工业大学 | Supported platinum catalyst, preparation method and preparation method of gemini quaternary ammonium salt |
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