CN108948062B - Preparation method of α -cyano acryloxy structure organic silicon compound with anthracene protection - Google Patents
Preparation method of α -cyano acryloxy structure organic silicon compound with anthracene protection Download PDFInfo
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- 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 System
- 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
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention relates to the field of organic chemistry, and aims to solve the problems of harsh reaction conditions, more byproducts and lower yield of a target product in the preparation of an organosilicon polymer with an anthracene-protected α -cyanoacrylate structure.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a preparation method of an anthracene-protected α -cyanoacryloxy structure-containing organic silicon compound.
Background
The organic silicon compound containing the α -cyanoacrylate structure protected by anthracene is an important intermediate for preparing the organic silicon compound with the α -cyanoacrylate structure, the organic silicon compound can be quickly crosslinked and cured in an anion polymerization mode under the action of moisture in air, the organic silicon material is endowed with the capability of quickly crosslinking and curing under a mild condition, and the organic silicon compound is widely applied to the fields of criminal investigation, information collection, bonding, sealing, leakage stoppage and the like which need to be quickly formed in situ.
Although anthracene protection and anthracene protection group removal organic silicon polymer containing α -cyanoacrylate structure and preparation method thereof are reported in literature, many challenges still face to chemically modifying organic silicon polymer to graft α -cyanoacrylate structure unit on chain end or side chain of organic silicon polymer, U.S. Pat. No. 3,137,34 discloses a method for grafting α -cyanoacrylate functional group to chain end or side chain of polysiloxane through condensation reaction between Si-OH and anthracene-protected α -cyanoacrylate (equation 1) or hydrosilylation reaction between Si-H and anthracene-protected α -cyanoacrylate (equation 2) by using linear polysiloxane containing Si-OH or Si-H functional group as substrate.
It is known that the phenomena of entanglement, wrapping and the like of a high molecular chain can prevent reaction sites in a polymer molecular chain from being unable to participate in reaction, so that the reaction conversion rate is not high, for the hydrosilylation reaction of unsaturated olefin, in addition to the addition reaction at the α position of the olefin, the addition reaction also exists at the B position of the olefin, namely competition between the Ma addition reaction and the anti-Ma addition reaction exists, so that the hydrosilylation product inevitably generates cis-isomer and trans-isomer with different structures, on the other hand, the conditions required by the hydrosilylation reaction are harsh, the yield is not high, and the hydrosilylation reaction can be carried out only when a Karstedt type hydrosilylation catalyst with the Pt mass fraction being more than 2.0 wt% is used, and even then the reaction yield is about 50%.
Reaction formula 1 condensation reaction preparation of polysiloxane containing anthracene-protected α -cyanoacryloxy structure
Reaction formula 2 hydrosilylation preparation of polysiloxane containing anthracene-protected α -cyanoacryloxy structure
Although the condensation reaction between Si-OH and anthracene-protected α -cyanoacrylate does not produce isomers, due to the fact that acyl chloride chemicals are high in toxicity and the half death rate LC50 of the acyl chloride chemicals is low in value, the preparation of anthracene-protected α -cyanoacrylate has certain safety risk.
Disclosure of Invention
In order to solve the problems of harsh reaction conditions, more byproducts and lower yield of target products in the existing preparation of an organic silicon polymer containing an anthracene-protected α -cyanoacrylate structure, the invention provides a preparation method of an organic silicon compound containing an anthracene-protected α -cyanoacrylate structure, and the preparation method has the characteristics of low energy consumption, small environmental pollution, safety, environmental protection, high yield, easy separation of products, simple process and equipment, low production cost and the like.
The chemical structural formula of the organosilicon compound containing the α -cyano acryloxy structure protected by anthracene is shown as (I),
in the formula, R1，R2，R3Are respectively and independently selected from R OR OR groups, and R is selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl.
The invention is realized by the following technical scheme that the preparation method of the organic silicon compound containing the α -cyano acryloxy structure protected by anthracene is prepared by adopting a two-step method:
(1) adding gamma-chloropropylsilane and α -cyano acrylic acid potassium salt protected by anthracene into an aprotic polar solvent, stirring and mixing, then adding a halogenated reaction catalyst and an esterification reaction catalyst into a reaction system, heating the materials and reacting at the temperature after the addition is finished, then cooling to room temperature, filtering the reaction product, and collecting filtrate to obtain an organic silicon compound solution containing α -cyano acrylic acyloxy structure protected by anthracene;
the gamma-chloropropyl silane is selected from one of gamma-chloropropyl trialkylsilane, gamma-chloropropyl alkyl dialkoxy silane, gamma-chloropropyl dialkyl alkoxy silane and gamma-chloropropyl trialkoxy silane, and the structure of the gamma-chloropropyl trialkoxy silane is shown in a formula (II),
in the formula, R1，R2，R3Each independently selected from alkyl R OR alkoxy OR, R is selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl;
preferably, the gamma-chloropropyl silane is selected from gamma-chloropropyl alkoxy silane; more preferably, the gamma-chloropropyl silane is selected from one of gamma-chloropropyl trimethoxy silane, gamma-chloropropyl triethoxy silane, gamma-chloropropyl methyl dimethoxy silane or gamma-chloropropyl methyl diethoxy silane.
The molar ratio of the gamma-chloropropylsilane to the anthracene-protected α -cyanoacrylate potassium salt is 0.5-5: 1, preferably, the molar ratio of the gamma-chloropropylsilane to the anthracene-protected α -cyanoacrylate potassium salt is 0.7-2: 1, and more preferably, the molar ratio of the gamma-chloropropylsilane to the anthracene-protected α -cyanoacrylate potassium salt is 0.95-1.15: 1.
The aprotic polar solvent is one or more selected from dimethyl sulfoxide (DMSO), acetonitrile, N, N-Dimethylformamide (DMF), N, N-Dimethylacetamide (DMAC), acetone and Hexamethylphosphoramide (HMP); preferably, the aprotic polar solvent is selected from one or two of DMF and DMAC; more preferably, the aprotic polar solvent is selected from DMF.
The dosage of the aprotic polar solvent is 3-15 times of the mass of α -potassium cyanoacrylate protected by anthracene, preferably, the dosage of the aprotic polar solvent is 5-10 times of the mass of α -potassium cyanoacrylate protected by anthracene, and more preferably, the dosage of the aprotic polar solvent is 6-9 times of the mass of α -potassium cyanoacrylate protected by anthracene.
The halogenation catalyst is selected from one of LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr and KI; preferably, the halogenation catalyst is selected from one of KBr or KI.
The dosage of the halogenation reaction catalyst is 5-25% of the mass of the anthracene-protected α -potassium cyanoacrylate salt, and preferably, the dosage of the halogenation reaction catalyst is 7.5-15% of the mass of the anthracene-protected α -potassium cyanoacrylate salt.
The esterification catalyst is selected from one of 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 3-dimethylaminopyridine, 4-dimethylaminopyridine and 2- (2-aminoethyl) pyridine; preferably, the esterification reaction catalyst is selected from one of 2-dimethylamino pyridine, 3-dimethylamino pyridine and 4-dimethylamino pyridine; more preferably, the esterification catalyst is selected from 4-dimethylaminopyridine.
The dosage of the esterification reaction catalyst is 0.1-10% of the mass of the anthracene-protected α -potassium cyanoacrylate salt, and preferably, the dosage of the esterification reaction catalyst is 0.5-5% of the mass of the anthracene-protected α -potassium cyanoacrylate salt.
The reaction temperature is 100-140 ℃, the reaction time is 0.5-5 h, preferably, the temperature is 110-130 ℃, and the reaction time is 1-4 h.
(2) Slowly dripping an organic silicon compound solution containing an anthracene-protected α -cyanoacrylate structure into a sodium chloride aqueous solution, standing for 2-4 h after dripping, removing a water layer after the product is settled, recovering an organic layer, dissolving the organic layer in halogenated alkane, repeatedly washing by using deionized water until the water phase is clear, colorless and transparent, then recovering the organic layer, removing water carried in the organic layer by using anhydrous sodium sulfate, filtering, and removing a solvent from the collected filtrate by adopting a reduced pressure distillation mode and the like to obtain the organic silicon compound containing the anthracene-protected α -cyanoacrylate structure.
The mass percentage of sodium chloride in the sodium chloride aqueous solution is 3-25%; preferably, the mass percentage of sodium chloride in the sodium chloride aqueous solution is 5-20%; more preferably, the mass percentage of the sodium chloride in the sodium chloride aqueous solution is 5-15%.
The using amount of the sodium chloride aqueous solution is 20-60 times of the mass of α -potassium cyanoacrylate protected by anthracene, preferably, the using amount of the sodium chloride aqueous solution is 25-50 times, more preferably 30-40 times of the mass of α -potassium cyanoacrylate protected by anthracene.
The halogenated alkane is selected from one of mono-substituted halogenated alkane, di-substituted halogenated alkane, tri-substituted halogenated alkane and tetra-substituted halogenated alkane, and preferably, the halogenated alkane is selected from di-substituted halogenated alkane; wherein, the alkane is selected from one of methane, ethane, propane, butane, pentane and hexane, preferably, the alkane is methane or ethane; more preferably, the haloalkane is dichloromethane.
The dosage of the halogenated alkane is 3-50 times of the mass of the α -potassium cyanoacrylate protected by anthracene, preferably, the dosage of the halogenated alkane is 5-40 times of the mass of the α -potassium cyanoacrylate protected by anthracene, and more preferably, the dosage of the halogenated alkane is 7-30 times of the mass of the α -potassium cyanoacrylate protected by anthracene.
The preparation method is carried out at room temperature, and the temperature is 20 +/-5 ℃.
The invention takes gamma-chloropropylsilane and α -cyano-acrylic acid potassium salt protected by anthracene as raw materials, prepares an organic silicon compound containing α -cyano-acrylic acyloxy structure protected by anthracene by condensation reaction, and has the following reaction formula:
the organosilicon compound containing the anthracene-protected α -cyanoacrylate structure can be prepared into an organosilicon polymer with the anthracene-protected α -cyanoacrylate structure by self-hydrolysis, condensation and other reactions or co-hydrolysis, condensation and other reactions with other organosilicon monomers, and the organosilicon polymer with the anthracene-protected α -cyanoacrylate structure can be obtained by removing the anthracene protecting group, or the organosilicon polymer with the rapid crosslinking and curing can be prepared by removing the anthracene protecting group from the organosilicon compound containing the anthracene-protected α -cyanoacrylate structure and then by self-hydrolysis, condensation and other reactions or co-hydrolysis, condensation and other reactions with other organosilicon monomers.
Compared with the prior art, the method has the beneficial effects that the reaction condition is mild, the product composition is single, the synthetic yield of the organic silicon compound containing the α -cyano-acryloxy structure protected by anthracene is high, the separation and purification are easy, and the industrialization is easy to realize.
Drawings
FIG. 1 is a 1H-NMR spectrum of anthracene-protected α -cyanoacryloxypropyltriethoxysilane;
FIG. 2 is a 1H-NMR spectrum of anthracene-protected α -cyanoacryloxypropylmethyldiethoxysilane.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the present invention. The starting materials used in the examples are either commercially available or prepared by conventional methods.
Example 1
Adding 20mL of DMF solvent into a 100mL three-neck flask provided with a condenser, a thermometer and an electromagnetic stirrer, adding 3.13g (0.01mol) of anthracene-protected α -cyanoacrylate potassium salt, 2.48g (0.0103mol) of gamma-chloropropyltriethoxysilane, 0.311g of potassium iodide serving as a halogenated reaction catalyst, 0.0319g of 4-dimethylaminopyridine serving as an esterification reaction catalyst under stirring at room temperature, heating to 120 ℃, reacting at the temperature for 2h, cooling to room temperature, filtering a crude reaction product to remove a byproduct KCl, slowly dropwise adding the collected filtrate into 100mL of a sodium chloride aqueous solution with a mass fraction of 12% under stirring at a speed of 1-2 drops per second, standing for 2h after dropwise adding, removing an upper layer after the product is settled, adding 40mL of dichloromethane dissolved product into the collected organic layer, adding 80mL of deionized water into the dichloromethane solution to wash away residual DMF solvent in the product, then again removing the remaining organic layer, repeating the steps for 7 times until an aqueous layer is removed, collecting a clear filtrate, filtering a clear filtrate, adding a distilled water layer into the dichloromethane dissolved product, filtering a filtrate without adding 3.54 g of anthracene-52.4 g of anhydrous propyl protecting silane, and filtering to obtain a filtrate, and drying filtrate, wherein the filtrate is obtained.
Example 2
Adding 50mL of DMAC (N, N-dimethylacetamide) solvent into a 250mL three-necked flask provided with a condenser, a thermometer and an electromagnetic stirrer, adding 3.13g (0.01mol) of anthracene-protected α -cyanoacrylate potassium salt, 11.91g (0.0495mol) of gamma-chloropropyltriethoxysilane, 0.783g of potassium bromide serving as a halogenation catalyst and 0.1565g of 2-dimethylaminopyridine serving as an esterification catalyst under stirring at room temperature, then heating to 120 ℃, reacting at the temperature for 5h, then cooling to room temperature, filtering the crude reaction product to remove a byproduct, slowly adding 1-2 drops of the collected filtrate per second into 180mL of 13% sodium chloride aqueous solution under stirring, standing for 2h after the addition is completed, separating to remove an upper aqueous layer after the product is settled, adding 110mL of dichloromethane to the collected organic layer to dissolve the product, adding 180mL of deionized water into the dichloromethane solution, washing away residual DMAC solvent in the product, removing the aqueous layer by separating again until the organic layer is remained, distilling again until the aqueous layer is 8 times, repeating the distillation, filtering the reaction, collecting 357.89 g of clear aqueous layer, filtering the filtrate without adding water, drying to obtain 357-89 g of anthracene-free aqueous layer, and drying the filtrate to obtain a solution.
Example 3
Adding 20mL of DMSO (dimethyl sulfoxide) solvent into a 100mL three-necked flask provided with a condenser, a thermometer and an electromagnetic stirrer, adding 3.13g (0.01mol) of anthracene-protected α -cyanoacrylate potassium salt, 2.98g (0.015mol) of gamma-chloropropyltrimethoxysilane, 0.157g of sodium iodide serving as a halogenated reaction catalyst and 0.017g of 4-aminopyridine serving as an esterification reaction catalyst under stirring at room temperature, then heating to 100 ℃, reacting for 5h at the temperature, then cooling to room temperature, filtering a reaction crude product to remove a byproduct KCl, slowly dropwise adding the collected filtrate into 70mL of 9 mass percent sodium chloride aqueous solution under stirring at a speed of 1-2 drops per second, standing for 6h after dropwise addition, after the product is settled, removing an upper layer by liquid separation, adding 20mL of trichloromethane dissolved product into the collected organic layer, adding 90mL of deionized water into the trichloromethane solution, washing away residual solvent in the product, then removing an aqueous layer by liquid separation, repeating the aqueous layer 7 times until the aqueous layer is distilled, removing a clear filtrate, filtering to remove α g of the trichloromethane dissolved product, filtering, and drying to obtain 3532.82 g of clear aqueous solution of anthracene-free propyl-substituted anthracene, and collecting 3g of sodium sulfate.
Example 4
Adding 10mL of an LDMF solvent into a 50mL three-necked flask provided with a condenser, a thermometer and an electromagnetic stirrer, adding 1.57g (0.005mol) of an anthracene-protected α -cyanoacrylate potassium salt, 1.22g (0.0067mol) of gamma-chloropropylmethyldimethoxysilane, 0.156g of a halogenated reaction catalyst potassium iodide, 0.0056g of an esterification catalyst 2- (2-aminoethyl) pyridine under stirring at room temperature, then heating to 120 ℃, reacting at the temperature for 2 hours, cooling to room temperature, filtering a reaction crude product to remove a byproduct KCl, slowly dropwise adding the collected filtrate into 80mL of a 12% sodium chloride aqueous solution under stirring at a speed of 1-2 drops per second, standing for 4 hours after dropwise addition is completed, separating to remove an upper aqueous layer after the product is settled, adding 60mL of a 1, 2-dichloroethane dissolved product into the collected organic layer, adding 160mL of DMF into the 1, 2-dichloroethane dissolved product, washing off 160mL of DMF, then removing a residual solvent in the product, distilling to remove an aqueous layer again, collecting a clear filtrate, distilling to remove an organic layer, filtering a clear aqueous layer, filtering a clear filtrate, removing a filtrate of 1, filtering a supernatant of a filtrate, filtering a clear aqueous layer of acetone, filtering a clear solution, collecting a clear filtrate, removing a clear aqueous layer, drying a clear filtrate, removing a filtrate, adding 358 g of acetone, and filtering a clear filtrate, and filtering solution, and filtering a clear filtrate to obtain a clear filtrate, and filtering solution, and filtering a clear filtrate.
Example 5
Adding 40mL of hexamethylphosphoramide solvent into a 250mL three-neck flask provided with a condenser, a thermometer and an electromagnetic stirrer, adding 13.13g (0.042mol) of anthracene-protected α -cyano potassium acrylate, 12.66g (0.084mol) of gamma-chloropropyltrimethylsilane, 1.315g of potassium iodide serving as a halogenated reaction catalyst, 0.1314g of 4-aminopyridine serving as an esterification reaction catalyst under stirring at room temperature, heating to 130 ℃, reacting at the temperature for 4.5h, cooling to room temperature, filtering a reaction crude product to remove a byproduct KCl, slowly dropwise adding the collected filtrate into 400mL of 7% sodium chloride aqueous solution with a mass fraction at a speed of 1-2 drops per second, standing for 2h after dropwise addition, removing an upper layer after the product is settled, adding 40mL of dichloromethane dissolved product into the collected organic layer, adding 160mL of deionized water into the dichloromethane solution, washing off residual hexamethylphosphoramide solvent in the product, then again removing an aqueous layer, repeating 9 times until the aqueous layer is removed, collecting a clear filtrate, filtering a clear filtrate, adding 31.91 g of dichloromethane dissolved product into the clear organic layer, and drying to obtain a filtrate, adding 3683- α g of anthracene-35 g of anhydrous propyl protecting sodium sulfate, and standing to obtain a filtrate, wherein the anthracene-free solution.
Example 6
Adding 10mL hexamethylphosphoramide solvent into a 50mL three-neck flask provided with a condenser, a thermometer and an electromagnetic stirrer, adding 1.57g (0.005mol) anthracene-protected α -cyanoacrylate potassium salt, 0.542g (0.003mol) gamma-chloropropyldimethylethoxysilane, 0.156g lithium bromide serving as a halogenated reaction catalyst and 0.0158g 3-aminopyridine serving as an esterification reaction catalyst under stirring at room temperature, heating to 110 ℃, reacting for 4h at the temperature, cooling to room temperature, filtering a reaction crude product to remove a byproduct KCl, slowly dropwise adding the collected filtrate into 60mL sodium chloride aqueous solution with a mass fraction of 25% under stirring at a speed of 1-2 drops per second, standing for 2h after dropwise addition, separating to remove an upper layer after the product is settled, adding 35mL carbon tetrachloride dissolved product into the collected organic layer, adding 70mL deionized water into the collected deionized water solution, washing off residual hexamethylphosphoramide solvent in the product, then again separating to remove an organic layer, repeating 7 times until an aqueous layer is removed, filtering a transparent carbon tetrachloride solution, collecting α g of transparent filtrate, filtering the filtrate without adding propylene oxide, drying, and collecting 355.79 g of anhydrous propyl anthracene-3 g filtrate, and obtaining anthracene-free sodium sulfate.
Example 7
Adding 20mL of DMF solvent into a 100mL three-neck flask provided with a condenser, a thermometer and an electromagnetic stirrer, adding 2.82g (0.009mol) of anthracene-protected α -cyanoacrylate potassium salt, 2.17g (0.009mol) of gamma-chloropropyltriethoxysilane, 0.173g of potassium iodide serving as a halogenated reaction catalyst, 0.0173g of 4-dimethylaminopyridine serving as an esterification reaction catalyst under stirring at room temperature, then heating to 120 ℃, reacting at the temperature for 1h, then cooling to room temperature, filtering out a crude reaction product to remove a byproduct KCl, slowly dropwise adding the collected filtrate into 100mL of 6 mass percent aqueous sodium chloride solution under stirring at a speed of 1-2 drops per second, standing for 2h after dropwise addition, after the product is settled, carrying out liquid separation to remove an upper layer, adding 45mL of dichloromethane dissolved product into the collected organic layer, adding 90mL of deionized water into the dichloromethane solution, washing out residual DMF solvent washing out liquid separation to remove the remaining organic layer, repeating the steps for 9 times until an aqueous reaction layer is removed, collecting a clear filtrate, filtering the filtrate, adding a clear filtrate into the dichloromethane dissolved product, carrying out liquid distillation, filtering, collecting a filtrate, carrying out liquid separation to obtain a filtrate, and carrying out filtration to obtain a filtrate, wherein the filtrate, the filtrate has a filtrate, the.
Example 8
Adding 20mL of DMF solvent into a 100mL three-neck flask provided with a condenser, a thermometer and an electromagnetic stirrer, adding 3.13g (0.01mol) of anthracene-protected α -cyanoacrylate potassium salt, 2.11g (0.01mol) of gamma-chloropropylmethyldiethoxysilane, 0.316g of potassium iodide serving as a halogenated reaction catalyst and 0.0310g of 4-dimethylaminopyridine serving as an esterification reaction catalyst under stirring at room temperature, heating to 120 ℃, reacting at the temperature for 2h, cooling to room temperature, filtering the reaction crude product to remove a byproduct KCl, slowly dropwise adding the collected filtrate into 100mL of 7% sodium chloride aqueous solution with a mass fraction at a speed of 1-2 drops per second, standing for 2h after dropwise addition, separating to remove an upper layer after the product is settled, adding 45mL of dichloromethane to dissolve the collected organic layer, adding 100mL of deionized water into the dichloromethane solution, washing off the residual DMF solvent in the product, then again separating to remove the aqueous layer, repeating the steps for 8 times until the aqueous layer is removed, collecting a clear filtrate, filtering, adding 3508 g of dichloromethane to the clear filtrate, filtering, and drying to obtain 3508 g of anhydrous propyl-free methyl anthracene-3.08 sodium sulfate.
The 1H-NMR spectrum of anthracene-protected α -cyanoacryloxypropyltriethoxysilane prepared in examples 1, 2, and 7 is shown in FIG. 1. the 1H-NMR spectrum of anthracene-protected α -cyanoacryloxypropylmethyldiethoxysilane prepared in example 8 is shown in FIG. 2.
Claims (9)
1. A preparation method of an anthracene-protected α -cyanoacryloxy structure-containing organic silicon compound is characterized by comprising the following steps:
(1) adding gamma-chloropropylsilane and α -cyano acrylic acid potassium salt protected by anthracene into an aprotic polar solvent, stirring and mixing, then adding a halogenated reaction catalyst and an esterification reaction catalyst into a reaction system, heating the materials and reacting at the temperature after the addition is finished, then cooling to room temperature, filtering a reaction product, and collecting filtrate to obtain an organic silicon compound solution containing α -cyano acrylic acyloxy structure protected by anthracene;
(2) dropwise adding an organosilicon compound solution containing an anthracene-protected α -cyano acryloxy structure into a sodium chloride aqueous solution, standing after dropwise adding until a product is settled, removing a water layer, and recovering an organic layer;
the aprotic polar solvent is selected from one or more of dimethyl sulfoxide, acetonitrile, N-dimethylformamide, N-dimethylacetamide, acetone and hexamethylphosphoramide;
the halogenation catalyst is selected from one of LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr and KI;
the esterification catalyst is selected from one of 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 3-dimethylaminopyridine, 4-dimethylaminopyridine and 2- (2-aminoethyl) pyridine;
the chemical structural formula of the organosilicon compound containing the α -cyano acryloxy structure protected by anthracene is shown as (I),
in the formula, R1, R2, R3Are respectively and independently selected from R OR OR groups, and R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl OR isobutyl.
2. The preparation method of the anthracene-protected α -cyanoacrylate-structure-containing organosilicon compound according to claim 1, wherein the gamma-chloropropylsilane in step (1) is one selected from gamma-chloropropyltrialkoxysilane, gamma-chloropropylalkyldialkoxysilane, gamma-chloropropyldialkylalkoxysilane and gamma-chloropropyltrialkoxysilane, and the molar ratio of the gamma-chloropropylsilane to the anthracene-protected α -potassium cyanoacrylate salt is 0.5-5: 1.
3. The method for preparing an anthracene-protected α -cyanoacrylate-containing organosilicon compound according to claim 1, wherein the amount of the aprotic polar solvent used in step (1) is 3 to 15 times the mass of the anthracene-protected α -potassium cyanoacrylate salt.
4. The method for preparing the anthracene-protected α -cyanoacrylate-based organosilicon compound according to claim 1, wherein the amount of the halogenation catalyst used in step (1) is 5% to 25% by mass of the anthracene-protected potassium α -cyanoacrylate salt.
5. The method for preparing the anthracene-protected α -cyanoacrylate-based organosilicon compound according to claim 1, wherein the esterification catalyst is used in an amount of 0.1% to 10% by mass of the anthracene-protected α -cyanoacrylate potassium salt.
6. The method for preparing the anthracene-protected α -cyanoacrylate-based organosilicon compound according to claim 1, wherein the temperature in step (1) is raised to 100-140 ℃ and the reaction time is 0.5-5 h.
7. The method for preparing the anthracene-protected α -cyanoacrylate-oxy structure-containing organosilicon compound according to claim 1, wherein the mass concentration of the aqueous sodium chloride solution in step (2) is 3% to 25%, and the amount of the aqueous sodium chloride solution is 20 to 60 times of the mass of the anthracene-protected α -cyanoacrylate potassium salt.
8. The method for preparing the anthracene-protected α -cyanoacrylate-based organosilicon compound according to claim 1, wherein the haloalkane in step (2) is selected from one of mono-substituted haloalkane, di-substituted haloalkane, tri-substituted haloalkane and tetra-substituted haloalkane, and the amount of the haloalkane is 3 to 50 times of the mass of the anthracene-protected α -potassium cyanoacrylate salt.
9. The method according to claim 8, wherein the alkane is selected from the group consisting of methane, ethane, propane, butane, pentane, and hexane.
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| EP2808707A1 (en) * | 2013-05-31 | 2014-12-03 | DSM IP Assets B.V. | Macromers comprising pendant polyoxazoline groups |
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| EP2808707A1 (en) * | 2013-05-31 | 2014-12-03 | DSM IP Assets B.V. | Macromers comprising pendant polyoxazoline groups |
| CN105247388A (en) * | 2013-05-31 | 2016-01-13 | 帝斯曼知识产权资产管理有限公司 | Macromers comprising pendant polyoxazoline groups and end groups |
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