CN113214310A - Preparation process of acryloxy silane oligomer - Google Patents
Preparation process of acryloxy silane oligomer Download PDFInfo
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- CN113214310A CN113214310A CN202110559472.0A CN202110559472A CN113214310A CN 113214310 A CN113214310 A CN 113214310A CN 202110559472 A CN202110559472 A CN 202110559472A CN 113214310 A CN113214310 A CN 113214310A
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- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000013067 intermediate product Substances 0.000 claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000460 chlorine Substances 0.000 claims abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 19
- 238000000746 purification Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 86
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- OKQXCDUCLYWRHA-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)Cl OKQXCDUCLYWRHA-UHFFFAOYSA-N 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- VEJBQZZDVYDUHU-UHFFFAOYSA-N ethenyl-hydroxy-dimethylsilane Chemical compound C[Si](C)(O)C=C VEJBQZZDVYDUHU-UHFFFAOYSA-N 0.000 claims description 6
- 238000010010 raising Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000000126 substance Substances 0.000 abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052697 platinum Inorganic materials 0.000 abstract description 6
- -1 platinum ions Chemical class 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000001282 organosilanes Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 4
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical compound [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention relates to the technical field of organosilane preparation, in particular to a preparation process of an acryloxy silane oligomer; in the invention, the 4, 4 '-dimethyl-2, 2' -bipyridyl and the chlorine ball are subjected to chemical reaction, and finally, the 4, 4 '-dimethyl-2, 2' -bipyridyl is successfully installed on the surface of the chlorine ball through chemical bonds; the product obtained after the reaction of the two components and platinum ions in the potassium chloroplatinite undergo a chemical reaction to form a coordination bond, so that the platinum ions are successfully loaded on the surface of the chlorine ball, the space density of the platinum ions on the surface of the chlorine ball is effectively increased, and the catalytic activity of the prepared catalyst is effectively enhanced; the catalyst is used for preparing an intermediate product, so that the synthesis efficiency of the acryloxy silane oligomer is improved; finally, the mixture is passed through D301 macroporous alkalescent styrene tertiary amino-N (CH)3)2The purification treatment of the acryloxysilane oligomer by the anion exchange resin further improves the purity of the acryloxysilane oligomer.
Description
Technical Field
The invention relates to the technical field of organosilane preparation, in particular to a preparation process of an acryloxy silane oligomer.
Background
Acryloxysilane oligomers are used in a wide range of daily life, for example: it can be used in unsaturated polyester composite material to raise the mechanical performance, electric performance and light transmittance of composite material, especially to raise the wet performance of composite material greatly. Moreover, the glass fiber is soaked and treated, so that the wet mechanical strength and the electrical property of the glass fiber reinforced composite material can be improved. In addition, it can be copolymerized with vinyl acetate and acrylic or methacrylic monomers, which are widely used in coatings, adhesives and sealants to provide excellent adhesion and durability.
Although the acryloxy silane oligomer prepared by the prior art can be used for preparing the acryloxy silane oligomer, the synthesis efficiency and the yield are relatively low; and the impurities are relatively more and the purity is lower.
Disclosure of Invention
Aiming at the technical problems in the background art, the invention provides a preparation process of an acryloyloxysilane oligomer, and the prepared acryloyloxysilane oligomer has high yield and relatively high synthesis efficiency; in addition, the prepared acryloxysilane oligomer has relatively less impurities and relatively higher purity.
Technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation process of an acryloxysilane oligomer, comprising the following steps:
firstly, preparing an intermediate product;
i, respectively putting materials into a glass reactor provided with a stirrer, a thermometer, a reflux cooler and a feeding funnel in a mass ratio of 1: 5-8: 3-5 parts of vinyl dimethyl silanol, hexamethylcyclotrisiloxane and acetonitrile; heating the mixed components in the glass reactor to 65-75 ℃ by using oil bath heating, mechanically mixing uniformly, adding a proper amount of catalyst into the uniformly mixed components, and stirring and reacting for 2-4 h at the temperature of 65-75 ℃;
II, after the reaction is finished, passivating the catalyst, and adding a proper amount of pyridine and toluene into the obtained mixed reaction liquid; after the mechanical stirring is uniform, dropwise adding a proper amount of 3-methacryloxypropyl dimethylchlorosilane into a glass reactor at the temperature of 20-30 ℃; in the dropping process, the temperature of reactants in the glass reactor is raised to 30-40 ℃; and pyridine hydrochloric acid salt is precipitated;
III, carrying out heat preservation reaction on reactants in the glass reactor for 40-80 min at the temperature of 35-45 ℃, washing and drying anhydrous sodium sulfate on obtained reaction products after the reaction is finished, extracting toluene from the reaction products under reduced pressure, and marking the obtained colorless, transparent and slightly viscous liquid as an intermediate product;
secondly, preparing an acryloxy silane oligomer;
according to the weight ratio of 1.4-1.6: 1, putting the obtained intermediate product and methylbenzene into a reaction kettle, putting an organic solution of chloroplatinic acid with the weight of 0.035-0.05% of the methylbenzene into the reaction kettle, uniformly mixing and stirring, raising the temperature in the reaction kettle to 75-85 ℃, slowly dripping 7.0-8.0% of trimethoxy silane with the weight of the intermediate product into the kettle at the temperature, and then carrying out heat preservation reaction at the temperature of 80-90 ℃ for 4-6 hours; naturally cooling the mixture to room temperature after the reaction is finished, adding active carbon for treatment, and then carrying out reduced pressure stripping to obtain toluene and the reacted trimethoxy silane, wherein the finally obtained colorless transparent slightly viscous liquid is the acryloxy silane oligomer;
thirdly, purifying the acryloxy silane oligomer;
and introducing the obtained acryloxy silane oligomer into an exchange column filled with adsorption resin, adsorbing and purifying the acryloxy silane oligomer for 3-5 hours at the temperature of 50-65 ℃, and obtaining the purified acryloxy silane oligomer after adsorption and purification.
Further, the preparation method of the catalyst in the step I comprises the following steps:
soaking a proper amount of chlorine spheres in N, N-dimethylformamide at the temperature of 30-40 ℃ for 25-40 h according to the solid-to-liquid ratio of 0.02-0.04 g/ml, and then adding 4, 4 '-dimethyl-2, 2' -bipyridine which is equal to the chlorine spheres; after uniformly mixing and stirring, heating the obtained mixed components to 90-110 ℃, carrying out heat preservation reaction for 1-2 h under the protection of nitrogen, filtering the obtained reaction solution when the reaction is finished, washing the obtained solid matters with ethanol for 3-5 times, transferring the solid matters into a constant-temperature drying oven, and carrying out drying treatment at 70-85 ℃;
after drying, mixing the mixture with potassium chloroplatinite according to the ratio of 2-3: 1, then adding the obtained mixed solid powder into a proper amount of organic solvent, carrying out reflux reaction for 6-10 hours under the protection of nitrogen, cooling and filtering the obtained reaction system after the reaction is finished, washing the obtained solid with acetone for 2-3 times, and then carrying out vacuum drying to constant weight to obtain the catalyst finished product.
Furthermore, the organic solvent is acetone, and the solid-liquid ratio of the mixed solid powder to the acetone is 0.04-0.06 g/ml.
Furthermore, in the step II, the adding amount of the pyridine is 10-15% of the hexamethylcyclotrisiloxane, and the adding amount of the toluene is 60-70% of the hexamethylcyclotrisiloxane.
Furthermore, in the step II, the addition amount of the 3-methacryloxypropyldimethylchlorosilane is 1.2-1.6 times of that of pyridine.
Further, in the step III, the washing method of the reaction product is as follows: washing the substrate with 1.0-1.5 mol/L sodium chloride aqueous solution for 1-2 times, and then washing the substrate with deionized water for 2-3 times.
Further, in the purification process of the acryloxysilane oligomer, the adsorption resin used is D301 macroporous weakly basic styrene tertiary amino-N (CH)3)2Is an anion exchange resin.
Further, in the purification process of the acryloxysilane oligomer, the flow rate is 0.3 to 2BV/h, and the ratio of diameter to height is 1: 4-6, and the sample adsorption time is 2-3 h.
Advantageous effects
Compared with the known public technology, the technical scheme provided by the invention has the following beneficial effects:
1. in the invention, chlorine spheres, 4 '-dimethyl-2, 2' -bipyridine, potassium platinochloride and the like are used as raw materials for preparing the catalyst, wherein the 4, 4 '-dimethyl-2, 2' -bipyridine and the chlorine spheres are subjected to chemical reaction, and finally, the 4, 4 '-dimethyl-2, 2' -bipyridine is successfully installed on the surfaces of the chlorine spheres through chemical bonds; the product obtained after the reaction of the two components and platinum ions in the potassium chloroplatinite undergo a chemical reaction to form a coordination bond, so that the platinum ions are successfully loaded on the surface of the chlorine ball, the space density of the platinum ions on the surface of the chlorine ball is effectively increased, and the catalytic activity of the prepared catalyst is effectively enhanced. The catalyst is used for preparing intermediate products, can effectively improve the reaction rate, and also improves the synthesis efficiency of the acryloxy silane oligomer.
2. The invention firstly takes vinyl dimethyl silanol, hexamethylcyclotrisiloxane, pyridine, 3-methacryloxypropyl dimethylchlorosilane and the like as raw materials for preparing an intermediate product, and the prepared intermediate product and trimethoxy silane generate chemistry to generate acryloxy silane oligomer under the catalysis of chloroplatinic acid. The yield of the prepared acryloxysilane oligomer is relatively high, and by-products generated in the reaction process are relatively less. Finally, the mixture is passed through D301 macroporous alkalescent styrene tertiary amino-N (CH)3)2The purification treatment of the acryloxy silane oligomer by the anion exchange resin further improves the purity of the acryloxy silane oligomer and effectively ensures the quality of the acryloxy silane oligomer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all 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.
The present invention will be further described with reference to the following examples.
Example 1
A preparation process of an acryloxysilane oligomer, comprising the following steps:
firstly, preparing an intermediate product;
i, respectively putting materials into a glass reactor provided with a stirrer, a thermometer, a reflux cooler and a feeding funnel in a mass ratio of 1: 5: 3 vinyl dimethyl silanol, hexamethylcyclotrisiloxane and acetonitrile; heating the mixed components in the glass reactor to 65 ℃ by using oil bath heating, mechanically and uniformly mixing, adding a proper amount of catalyst into the uniformly mixed components, and then stirring and reacting for 2 hours at the temperature of 65 ℃;
II, after the reaction is finished, passivating the catalyst, and adding a proper amount of pyridine and toluene into the obtained mixed reaction liquid; after the mechanical stirring is uniform, dropwise adding a proper amount of 3-methacryloxypropyl dimethylchlorosilane into a glass reactor at the temperature of 20 ℃; in the dropping process, the temperature of reactants in the glass reactor is raised to 30 ℃; and pyridine hydrochloric acid salt is precipitated;
III, keeping the temperature of reactants in the glass reactor at 35 ℃ for reacting for 40min, washing and drying anhydrous sodium sulfate on the obtained reaction product after the reaction is finished, extracting toluene from the reaction product under reduced pressure, and marking the obtained colorless, transparent and slightly viscous liquid as an intermediate product;
secondly, preparing an acryloxy silane oligomer;
according to the weight ratio of 1.4: 1, putting the obtained intermediate product and toluene into a reaction kettle, putting an organic solution of chloroplatinic acid with the weight of 0.035% of that of the toluene into the reaction kettle, uniformly mixing and stirring, raising the temperature in the reaction kettle to 75 ℃, slowly dripping 7.0% of trimethoxy silane with the weight of the intermediate product into the reaction kettle at the temperature, and then carrying out heat preservation reaction for 4 hours at the temperature of 80 ℃; naturally cooling the mixture to room temperature after the reaction is finished, adding active carbon for treatment, and then carrying out reduced pressure stripping to obtain toluene and the reacted trimethoxy silane, wherein the finally obtained colorless transparent slightly viscous liquid is the acryloxy silane oligomer;
thirdly, purifying the acryloxy silane oligomer;
and introducing the obtained acryloxy silane oligomer into an exchange column filled with adsorption resin, adsorbing and purifying the acryloxy silane oligomer for 3 hours at the temperature of 50 ℃, and obtaining the purified acryloxy silane oligomer after adsorption and purification.
The preparation method of the catalyst in the step I comprises the following steps:
soaking a proper amount of chlorine spheres in N, N-dimethylformamide at the temperature of 30 ℃ for 25h according to the solid-to-liquid ratio of 0.02g/ml, and then adding 4, 4 '-dimethyl-2, 2' -bipyridine which is equal to the amount of the chlorine spheres; after mixing and stirring uniformly, heating the obtained mixed components to 90 ℃, carrying out heat preservation reaction for 1h under the protection of nitrogen, filtering the obtained reaction solution while the reaction is hot after the reaction is finished, washing the obtained solid substance for 3 times by using ethanol, transferring the solid substance into a constant-temperature drying oven, and carrying out drying treatment at 70 ℃;
after drying, mixing the mixture with potassium chloroplatinite according to the weight ratio of 2: 1, then putting the obtained mixed solid powder into a proper amount of organic solvent, carrying out reflux reaction for 6 hours under the protection of nitrogen, after the reaction is finished, cooling and filtering the obtained reaction system, washing the obtained solid with acetone for 2 times, and then carrying out vacuum drying to constant weight to obtain the catalyst finished product.
The organic solvent is acetone, and the solid-liquid ratio of the mixed solid powder to the acetone is 0.04 g/ml.
In the step II, the adding amount of pyridine is 10% of hexamethylcyclotrisiloxane, and the adding amount of toluene is 60% of hexamethylcyclotrisiloxane.
In step II, the amount of 3-methacryloxypropyldimethylchlorosilane added is 1.2 times that of pyridine.
In the step III, the washing method of the reaction product comprises the following steps: the mixture was washed with 1.0mol/L aqueous sodium chloride solution 1 time and then with deionized water 2 times.
In the purification process of the acryloxysilane oligomer, the used adsorption resin is D301 macroporous alkalescent styrene tertiary amino-N (CH)3)2Is an anion exchange resin.
In the purification step of the acryloxysilane oligomer, the flow rate was 0.3BV/h, and the aspect ratio was 1: 4, the sample adsorption time is 2 h.
Example 2
A preparation process of an acryloxysilane oligomer, comprising the following steps:
firstly, preparing an intermediate product;
i, respectively putting materials into a glass reactor provided with a stirrer, a thermometer, a reflux cooler and a feeding funnel in a mass ratio of 1: 6: 4 vinyl dimethyl silanol, hexamethylcyclotrisiloxane and acetonitrile; heating the mixed components in the glass reactor to 70 ℃ by using oil bath heating, mechanically and uniformly mixing, adding a proper amount of catalyst into the uniformly mixed components, and then stirring and reacting for 3 hours at the temperature of 70 ℃;
II, after the reaction is finished, passivating the catalyst, and adding a proper amount of pyridine and toluene into the obtained mixed reaction liquid; after the mechanical stirring is uniform, dropwise adding a proper amount of 3-methacryloxypropyl dimethylchlorosilane into a glass reactor at the temperature of 25 ℃; in the dropping process, the temperature of reactants in the glass reactor is raised to 35 ℃; and pyridine hydrochloric acid salt is precipitated;
III, carrying out heat preservation reaction on reactants in the glass reactor for 60min at the temperature of 40 ℃, washing and drying anhydrous sodium sulfate on obtained reaction products after the reaction is finished, extracting toluene from the reaction products under reduced pressure, and marking the obtained colorless, transparent and slightly viscous liquid as an intermediate product;
secondly, preparing an acryloxy silane oligomer;
according to the weight ratio of 1.5: 1, putting the obtained intermediate product and toluene into a reaction kettle, putting an organic solution of chloroplatinic acid with the weight of 0.045% of that of the toluene into the reaction kettle, uniformly mixing and stirring, raising the temperature in the reaction kettle to 80 ℃, slowly dripping 7.5% of trimethoxy silane with the weight of the intermediate product into the reaction kettle at the temperature, and then carrying out heat preservation reaction for 5 hours at the temperature of 85 ℃; naturally cooling the mixture to room temperature after the reaction is finished, adding active carbon for treatment, and then carrying out reduced pressure stripping to obtain toluene and the reacted trimethoxy silane, wherein the finally obtained colorless transparent slightly viscous liquid is the acryloxy silane oligomer;
thirdly, purifying the acryloxy silane oligomer;
and introducing the obtained acryloxy silane oligomer into an exchange column filled with adsorption resin, adsorbing and purifying the acryloxy silane oligomer for 4 hours at the temperature of 60 ℃, and obtaining the purified acryloxy silane oligomer after adsorption and purification.
The preparation method of the catalyst in the step I comprises the following steps:
soaking a proper amount of chlorine spheres in N, N-dimethylformamide at the temperature of 35 ℃ for 32 hours according to the solid-to-liquid ratio of 0.03g/ml, and then adding 4, 4 '-dimethyl-2, 2' -bipyridine which is equal to the amount of the chlorine spheres; after mixing and stirring uniformly, raising the temperature of the obtained mixed components to 100 ℃, carrying out heat preservation reaction for 1.5h under the protection of nitrogen, filtering the obtained reaction solution when the reaction is finished, washing the obtained solid substance for 4 times by using ethanol, transferring the solid substance into a constant-temperature drying oven, and carrying out drying treatment at the atmosphere of 80 ℃;
after drying, the mixture is mixed with potassium chloroplatinite according to the weight ratio of 2.5: 1, then adding the obtained mixed solid powder into a proper amount of organic solvent, carrying out reflux reaction for 8 hours under the protection of nitrogen, cooling and filtering the obtained reaction system after the reaction is finished, washing the obtained solid with acetone for 2 times, and then carrying out vacuum drying to constant weight to obtain the catalyst finished product.
The organic solvent was acetone, and the solid-to-liquid ratio of the mixed solid powder to acetone was 0.05 g/ml.
In the step II, the adding amount of pyridine is 12% of hexamethylcyclotrisiloxane, and the adding amount of toluene is 65% of hexamethylcyclotrisiloxane.
In step II, the amount of 3-methacryloxypropyldimethylchlorosilane added is 1.4 times that of pyridine.
In the step III, the washing method of the reaction product comprises the following steps: the mixture was washed with 1.3mol/L aqueous sodium chloride solution 2 times and then with deionized water 2 times.
In the purification process of the acryloxysilane oligomer, the used adsorption resin is D301 macroporous alkalescent styrene tertiary amino-N (CH)3)2Is an anionAnd (4) exchanging resin.
In the purification step of the acryloxysilane oligomer, the flow rate is 1.2BV/h, and the aspect ratio is 1: and 5, the sample adsorption time is 2.5 h.
Example 3
A preparation process of an acryloxysilane oligomer, comprising the following steps:
firstly, preparing an intermediate product;
i, respectively putting materials into a glass reactor provided with a stirrer, a thermometer, a reflux cooler and a feeding funnel in a mass ratio of 1: 8: 5 vinyl dimethyl silanol, hexamethylcyclotrisiloxane and acetonitrile; heating the mixed components in the glass reactor to 75 ℃ by using oil bath heating, mechanically and uniformly mixing, adding a proper amount of catalyst into the uniformly mixed components, and then stirring and reacting for 4 hours at the temperature of 75 ℃;
II, after the reaction is finished, passivating the catalyst, and adding a proper amount of pyridine and toluene into the obtained mixed reaction liquid; after the mechanical stirring is uniform, dropwise adding a proper amount of 3-methacryloxypropyl dimethylchlorosilane into a glass reactor at the temperature of 30 ℃; in the dropping process, the temperature of reactants in the glass reactor is raised to 40 ℃; and pyridine hydrochloric acid salt is precipitated;
III, carrying out heat preservation reaction on reactants in the glass reactor at the temperature of 45 ℃ for 80min, washing and drying anhydrous sodium sulfate on obtained reaction products after the reaction is finished, extracting toluene from the reaction products under reduced pressure, and marking the obtained colorless, transparent and slightly viscous liquid as an intermediate product;
secondly, preparing an acryloxy silane oligomer;
according to the weight ratio of 1.6: 1, putting the obtained intermediate product and toluene into a reaction kettle, putting an organic solution of chloroplatinic acid with the weight of 0.05 percent of the toluene into the reaction kettle, mixing and stirring uniformly, raising the temperature in the reaction kettle to 85 ℃, slowly dripping trimethoxy silane with the weight of 8.0 percent of the intermediate product into the reaction kettle at the temperature, and then carrying out heat preservation reaction for 6 hours at the temperature of 90 ℃; naturally cooling the mixture to room temperature after the reaction is finished, adding active carbon for treatment, and then carrying out reduced pressure stripping to obtain toluene and the reacted trimethoxy silane, wherein the finally obtained colorless transparent slightly viscous liquid is the acryloxy silane oligomer;
thirdly, purifying the acryloxy silane oligomer;
and (3) introducing the obtained acryloxy silane oligomer into an exchange column filled with adsorption resin, adsorbing and purifying the acryloxy silane oligomer for 5 hours at the temperature of 65 ℃, and obtaining the purified acryloxy silane oligomer after adsorption and purification.
The preparation method of the catalyst in the step I comprises the following steps:
soaking a proper amount of chlorine spheres in N, N-dimethylformamide at the temperature of 40 ℃ for 40h according to the solid-to-liquid ratio of 0.04g/ml, and then adding 4, 4 '-dimethyl-2, 2' -bipyridine which is equal to the amount of the chlorine spheres; after mixing and stirring uniformly, heating the obtained mixed components to 110 ℃, carrying out heat preservation reaction for 2 hours under the protection of nitrogen, filtering the obtained reaction solution while the reaction is hot after the reaction is finished, washing the obtained solid substance for 5 times by using ethanol, transferring the solid substance into a constant-temperature drying oven, and carrying out drying treatment at 85 ℃;
after drying, mixing the mixture with potassium chloroplatinite according to the proportion of 3: 1, then putting the obtained mixed solid powder into a proper amount of organic solvent, carrying out reflux reaction for 10 hours under the protection of nitrogen, after the reaction is finished, cooling and filtering the obtained reaction system, washing the obtained solid with acetone for 3 times, and then carrying out vacuum drying to constant weight to obtain the catalyst finished product.
The organic solvent was acetone, and the solid-to-liquid ratio of the mixed solid powder to acetone was 0.06 g/ml.
In the step II, the adding amount of pyridine is 15% of hexamethylcyclotrisiloxane, and the adding amount of toluene is 70% of hexamethylcyclotrisiloxane.
In step II, the amount of 3-methacryloxypropyldimethylchlorosilane added is 1.6 times that of pyridine.
In the step III, the washing method of the reaction product comprises the following steps: the mixture was washed with 1.5mol/L aqueous sodium chloride solution 2 times and then with deionized water 3 times.
In the purification process of the acryloxysilane oligomer, the used adsorption resin is D301 macroporous alkalescent styrene tertiary amino-N (CH)3)2Is an anion exchange resin.
In the purification step of the acryloxysilane oligomer, the flow rate is 2BV/h, and the aspect ratio is 1: and 6, the sample adsorption time is 3 h.
Comparative example 1: the acryloxysilane oligomer prepared by the preparation process provided in example 1 of the present invention was different in that: the catalyst prepared by the invention is not used in the preparation process of the acryloxysilane oligomer, and the prepared acryloxysilane oligomer is not subjected to purification treatment;
performance testing
The acryloyloxysilane oligomers prepared by examples 1 to 3 of the present invention were respectively referred to as experimental examples 1 to 3; the acryloxysilane oligomer prepared by comparative example 1 was respectively designated as comparative example 1; the purity and yield of the resulting acryloxysilane oligomer product were then determined separately and the data reported in the following table:
by comparing the relevant data in the above table it can be seen that: compared with the comparative example 1, the acryloxy silane oligomer prepared by the invention has higher yield and higher synthesis efficiency; in addition, the prepared acryloxysilane oligomer has relatively less impurities and relatively higher purity. Therefore, the preparation process of the acryloyloxysilane oligomer provided by the invention has wider market prospect and is more suitable for popularization.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (8)
1. A preparation process of an acryloxysilane oligomer is characterized by comprising the following steps:
firstly, preparing an intermediate product;
i, respectively putting materials into a glass reactor provided with a stirrer, a thermometer, a reflux cooler and a feeding funnel in a mass ratio of 1: 5-8: 3-5 parts of vinyl dimethyl silanol, hexamethylcyclotrisiloxane and acetonitrile; heating the mixed components in the glass reactor to 65-75 ℃ by using oil bath heating, mechanically mixing uniformly, adding a proper amount of catalyst into the uniformly mixed components, and stirring and reacting for 2-4 h at the temperature of 65-75 ℃;
II, after the reaction is finished, passivating the catalyst, and adding a proper amount of pyridine and toluene into the obtained mixed reaction liquid; after the mechanical stirring is uniform, dropwise adding a proper amount of 3-methacryloxypropyl dimethylchlorosilane into a glass reactor at the temperature of 20-30 ℃; in the dropping process, the temperature of reactants in the glass reactor is raised to 30-40 ℃; and pyridine hydrochloric acid salt is precipitated;
III, carrying out heat preservation reaction on reactants in the glass reactor for 40-80 min at the temperature of 35-45 ℃, washing and drying anhydrous sodium sulfate on obtained reaction products after the reaction is finished, extracting toluene from the reaction products under reduced pressure, and marking the obtained colorless, transparent and slightly viscous liquid as an intermediate product;
secondly, preparing an acryloxy silane oligomer;
according to the weight ratio of 1.4-1.6: 1, putting the obtained intermediate product and methylbenzene into a reaction kettle, putting an organic solution of chloroplatinic acid with the weight of 0.035-0.05% of the methylbenzene into the reaction kettle, uniformly mixing and stirring, raising the temperature in the reaction kettle to 75-85 ℃, slowly dripping 7.0-8.0% of trimethoxy silane with the weight of the intermediate product into the kettle at the temperature, and then carrying out heat preservation reaction at the temperature of 80-90 ℃ for 4-6 hours; naturally cooling the mixture to room temperature after the reaction is finished, adding active carbon for treatment, and then carrying out reduced pressure stripping to obtain toluene and the reacted trimethoxy silane, wherein the finally obtained colorless transparent slightly viscous liquid is the acryloxy silane oligomer;
thirdly, purifying the acryloxy silane oligomer;
and introducing the obtained acryloxy silane oligomer into an exchange column filled with adsorption resin, adsorbing and purifying the acryloxy silane oligomer for 3-5 hours at the temperature of 50-65 ℃, and obtaining the purified acryloxy silane oligomer after adsorption and purification.
2. The process of claim 1, wherein the catalyst of step i is prepared by the steps of:
soaking a proper amount of chlorine spheres in N, N-dimethylformamide at the temperature of 30-40 ℃ for 25-40 h according to the solid-to-liquid ratio of 0.02-0.04 g/ml, and then adding 4, 4 '-dimethyl-2, 2' -bipyridine which is equal to the chlorine spheres; after uniformly mixing and stirring, heating the obtained mixed components to 90-110 ℃, carrying out heat preservation reaction for 1-2 h under the protection of nitrogen, filtering the obtained reaction solution when the reaction is finished, washing the obtained solid matters with ethanol for 3-5 times, transferring the solid matters into a constant-temperature drying oven, and carrying out drying treatment at 70-85 ℃;
after drying, mixing the mixture with potassium chloroplatinite according to the ratio of 2-3: 1, then adding the obtained mixed solid powder into a proper amount of organic solvent, carrying out reflux reaction for 6-10 hours under the protection of nitrogen, cooling and filtering the obtained reaction system after the reaction is finished, washing the obtained solid with acetone for 2-3 times, and then carrying out vacuum drying to constant weight to obtain the catalyst finished product.
3. The process for preparing an acryloxysilane oligomer according to claim 2, characterized in that: the organic solvent is acetone, and the solid-liquid ratio of the mixed solid powder to the acetone is 0.04-0.06 g/ml.
4. The process for preparing an acryloxysilane oligomer according to claim 1, characterized in that: in the step II, the input amount of pyridine is 10-15% of hexamethylcyclotrisiloxane, and the input amount of toluene is 60-70% of hexamethylcyclotrisiloxane.
5. The process for preparing an acryloxysilane oligomer according to claim 1, characterized in that: in the step II, the addition amount of the 3-methacryloxypropyl dimethylchlorosilane is 1.2-1.6 times of that of pyridine.
6. The process for preparing an acryloxysilane oligomer according to claim 1, wherein in the step III, the reaction product is washed by: washing the substrate with 1.0-1.5 mol/L sodium chloride aqueous solution for 1-2 times, and then washing the substrate with deionized water for 2-3 times.
7. The process for preparing an acryloxysilane oligomer according to claim 1, characterized in that: in the purification process of the acryloxysilane oligomer, the used adsorption resin is D301 macroporous alkalescent styrene tertiary amino-N (CH)3)2Is an anion exchange resin.
8. The process for preparing an acryloxysilane oligomer according to claim 1, characterized in that: in the purification process of the acryloxy silane oligomer, the flow rate is 0.3-2 BV/h, and the diameter-height ratio is 1: 4-6, and the sample adsorption time is 2-3 h.
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