WO2023019667A1 - Method for preparing functionalized disiloxane - Google Patents
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- WO2023019667A1 WO2023019667A1 PCT/CN2021/118426 CN2021118426W WO2023019667A1 WO 2023019667 A1 WO2023019667 A1 WO 2023019667A1 CN 2021118426 W CN2021118426 W CN 2021118426W WO 2023019667 A1 WO2023019667 A1 WO 2023019667A1
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- the invention relates to a preparation method of functionalized disiloxane, which belongs to the technical field of synthesis of organosilicon intermediates.
- Functionalized disiloxane is a common downstream product of silicone, which plays an important role in the production of silicone products, pharmaceuticals and chemical industries.
- functionalized disiloxane can be used as a polysiloxane end-capping agent, medical defoamer, and silicone rubber additive in the production of silicone products, and can be used as a cleaning agent, release agent, and phobic agent in organic chemical and pharmaceutical production. Water agent, lubricant for equipment and instrument damping fluid, etc.
- the former method is to first synthesize small molecules containing hydrolyzable units (Si-X, X is Cl, OR, R is methyl, ethyl, etc.), and then hydrolyzed and condensed to obtain them.
- This method is simple to synthesize and has high efficiency, there are some disadvantages, such as the preparation of disiloxane by hydrolysis and condensation of Si-Cl, HCl will be generated during the hydrolysis process, and the post-treatment will cause environmental pollution, and some functional groups are not suitable for this method. .
- the latter method is to prepare disiloxanes with active units first, and then further functionalize them to prepare novel disiloxanes.
- This method is currently widely used, such as 1,3-aminopropyl-1,1,3,3-tetramethyldisiloxane, acryloyloxymethyl or propyldisiloxane, in which acryloyloxy Methyldisiloxane is prepared by reacting 1,3-chloromethyl-1,1,3,3-tetramethyldisiloxane with potassium acrylate under the action of catalyst.
- hydroxyalkyl disiloxane as an important class of silicone products, is used to prepare hydroxyalkyl-terminated polysiloxane, and is one of the important raw materials for preparing special silicone copolymers by copolymerization with other organic polymers.
- the method of preparing functionalized disiloxanes from hydroxyhydrocarbyl disiloxanes is mainly through the reaction of hydroxyl groups with isocyanate or epoxy groups to obtain new functionalized disiloxanes.
- the types of oxanes are limited, and there is an urgent need to develop new methods that utilize hydroxyl groups to prepare novel functionalized disiloxanes.
- the acid produced by the hydrolysis method is more harmful to the environment, and the waste liquid after treatment cannot be reused, and the functional group is not suitable for this method.
- the types of disiloxanes synthesized by existing methods are limited, and it is impossible to obtain special functionalized disiloxanes.
- the present invention proposes a new method for preparing functionalized disiloxanes.
- a method for preparing functionalized disiloxanes that is, using hydroxyhydrocarbyl disiloxanes and unsaturated olefins with electron-withdrawing groups as basic raw materials, under the catalysis of catalysts, to prepare disiloxanes with different functionalizations. silicone.
- the hydroxyhydrocarbyl disiloxane and the unsaturated olefin with an electron-withdrawing group are dissolved in an organic solvent for the reaction, and the reaction can also be carried out without a solvent.
- R 1 , R 2 , R 3 , and R 4 are independently selected from C 1 -C 18 chain alkanes or aromatic hydrocarbons; further preferably, the alkane is selected from straight chain or Branched chain alkanes or cycloalkanes;
- R 5 is a C 1 -C 18 chain alkane or an alkane or aromatic hydrocarbon with a heteroatom; more preferably, the heteroatom is O, S, N.
- R 1 , R 2 , R 3 , R 4 , R 5 may be the same or different;
- the EWG represents an electron-withdrawing group; preferably, the electron-withdrawing group is selected from a nitrile group, an acrylate group, a sulfone group, a nitro group, a substituent of an acrylate derivative, an amide group, and the like.
- the unsaturated olefins with electron-withdrawing groups are double bond compounds
- R 13 is H or R 8 , and R 8 is a C 1 to C 18 chain alkyl group or a hydrocarbon group with heteroatoms such as O and S, and can also be an aromatic hydrocarbon group or a cycloalkane;
- R 6 , R 7 , R 8 are H or C 1 ⁇ C 18 chain alkyl groups or hydrocarbon groups with heteroatoms such as O and S, or aromatic hydrocarbon groups or cycloalkanes.
- R 6 , R 7 and R 8 may be the same or different;
- R 9 , R 10 , R 11 , and R 12 are C 1 -C 18 chain alkyl groups, or hydrocarbon groups with heteroatoms such as O and S, In addition, it can also be an aromatic hydrocarbon group or a cycloalkane, and R 9 , R 10 , R 11 , and R 12 can be the same or different; the protection scope of this invention is not limited thereto.
- R 1 , R 2 , R 3 , and R 4 are C 1 -C 18 chain alkyl groups or hydrocarbon groups with heteroatoms such as O and S, and R 5 It is a C 1 -C 18 chain alkyl group, and it can also be a hydrocarbon group with heteroatoms such as O and S, as well as cycloalkane and aromatic hydrocarbon.
- R 1 , R 2 , R 3 , R 4 , and R 5 may be the same or different.
- the molar ratio of hydroxyhydrocarbyl disiloxane to unsaturated olefins with electron-withdrawing groups is 1:2-5;
- the catalyst is added in an amount of 5 mol% to 20 mol% of the total molar weight of the reaction raw materials.
- the catalyst is selected from inorganic bases, organic bases, chiral phosphoric acid or metal complexes;
- the inorganic base is sodium carbonate or cesium carbonate;
- the organic base is 4-dimethylaminopyridine, phosphazene base, triphenylphosphine or potassium tert-butoxide;
- the metal complex is One or more of ytterbium trifluoromethanesulfonate (Yb(OTf) 3 ) or metal N-heterocyclic carbenes (NHCs) are mixed.
- the organic solvent is one or a mixture of tetrahydrofuran, dichloromethane, acetonitrile, N,N-dimethylformamide, toluene, and chloroform.
- the reaction temperature is 20-120°C.
- the reaction time is 0.5-24 hours.
- the preparation method of functionalized disiloxane comprises steps as follows:
- the reaction is based on the hydroxyl-double bond addition reaction, that is, the nucleophile with active hydrogen undergoes a conjugated addition reaction with the active ⁇ -system.
- the nucleophilic acceptor in this reaction system is an oxygen atom, also known as oxa Michael addition, this reaction can efficiently increase the utilization rate of hydroxyl and double bonds, and it is better used in the field of small molecule synthesis.
- the preparation method of the functionalized disiloxane of the present invention is simple, the reaction is fast, efficient, and the conversion rate is high, and the functionalized disiloxane with different functional groups can be obtained, which is the preparation method of the functionalized disiloxane and the preparation of the polysiloxane.
- the modification provides a favorable method basis and has a good prospect for further development.
- Fig. 1 is the NMR spectrum figure of target product A obtained in Example 1.
- Fig. 2 is the NMR spectrum of the target product B obtained in Example 2.
- Fig. 3 is the NMR spectrum of the target product C obtained in Example 3.
- the dosage of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.212 g of acrylonitrile, catalyst phosphazene base t- BuP 2 0.0735g, tetrahydrofuran 10mL, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were added to the In the three-neck flask that has been circulated by the melting pump, stir at room temperature for 4 hours under anhydrous and anaerobic conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, Filtration, rotary evaporation to remove the organic solvent, and the obtained product is the target functionalized disiloxane A.
- the composition of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.4246 g of methyl vinyl sulfone, and 4- Dimethylaminopyridine 0.0732g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, methyl vinyl sulfone and catalyst were added to the In the three-neck flask that has been circulated by the freeze-thaw pump three times, stir at 80°C for 12 hours under anhydrous and oxygen-free conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, and add anhydrous sulfuric acid Dried over magnesium, filtered, rotary evaporated to remove the organic solvent, purified by column chromatography, and the obtained product was the target functionalized disiloxane B.
- the dosage of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.6728 g of phenyl vinyl sulfone, and 4- Dimethylaminopyridine 0.0488g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were successively added to the In the three-neck flask that has been circulated by the pump, stir at room temperature for 4 hours under anhydrous and oxygen-free conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, filter , the organic solvent was removed by rotary evaporation, and purified by column chromatography, the obtained product was the target functionalized disiloxane C.
- the composition of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.4 g of ethyl acrylate, catalyst 4-dimethyl Aminopyridine 0.0732g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were sequentially added to the mixture after three freeze-thaw pump cycles In the three-neck flask that has been passed, stir at room temperature for 4 hours under anhydrous and oxygen-free conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, filter, spin The organic solvent was evaporated and purified by column chromatography, and the obtained product was the target functionalized disiloxane.
- the dosage of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.396 g of N,N-dimethylacrylamide , Potassium tert-butoxide 0.0224g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were sequentially added to the In the three-neck flask that has been circulated by the melting pump, stir at room temperature for 4 hours under anhydrous and anaerobic conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, Filtration, rotary evaporation to remove the organic solvent, and column chromatography purification, the obtained product is the target functionalized disiloxane.
- the composition of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.657 g of vinyl phosphate diethyl ester, catalyst phosphine Nitrile base t-BuP2 0.0735g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were added successively to the In the three-neck flask that has been circulated by the melting pump, stir at room temperature for 4 hours under anhydrous and oxygen-free conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, Filtration, rotary evaporation to remove the organic solvent, and column chromatography purification, the obtained product is the target functionalized disiloxane.
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Abstract
Description
本发明涉及一种官能化二硅氧烷的制备方法，属于有机硅中间体的合成技术领域。The invention relates to a preparation method of functionalized disiloxane, which belongs to the technical field of synthesis of organosilicon intermediates.
官能化二硅氧烷是一类常见的有机硅下游产品，在有机硅产品生产、医药化工等领域发挥着重要作用。例如官能化二硅氧烷在有机硅产品生产中可作为聚硅氧烷的封端剂、医用消泡剂、硅橡胶添加剂，在有机化工及医药生产中能作为清洗剂、脱模剂、憎水剂、设备器械用润滑剂以及仪表阻尼液等。Functionalized disiloxane is a common downstream product of silicone, which plays an important role in the production of silicone products, pharmaceuticals and chemical industries. For example, functionalized disiloxane can be used as a polysiloxane end-capping agent, medical defoamer, and silicone rubber additive in the production of silicone products, and can be used as a cleaning agent, release agent, and phobic agent in organic chemical and pharmaceutical production. Water agent, lubricant for equipment and instrument damping fluid, etc.
制备官能化二硅氧烷的方法主要有两种，一种是直接水解法，一种是利用现有的二硅氧烷进行功能化。前一种方法是首先合成含有可水解单元(Si-X，X为Cl、OR，R为甲基、乙基等)的小分子，然后水解缩合得到。此方法虽然合成简单，效率高，但存在一些缺点，如Si-Cl通过水解缩合制备二硅氧烷，伴随水解过程会有HCl生成，后处理会造成环境污染，且有些官能团不适用于此方法。后一种方法是先制备带有活性单元的二硅氧烷，然后再进一步功能化制备新型二硅氧烷。此方法目前应用较多，例如1,3-氨丙基-1,1,3,3-四甲基二硅氧烷、丙烯酰氧基甲基或丙基二硅氧烷，其中丙烯酰氧基甲基二硅氧烷是利用1,3-氯甲基-1,1,3,3-四甲基二硅氧烷与丙烯酸钾在催化剂作用下反应制得。There are two main methods for preparing functionalized disiloxanes, one is direct hydrolysis, and the other is functionalization using existing disiloxanes. The former method is to first synthesize small molecules containing hydrolyzable units (Si-X, X is Cl, OR, R is methyl, ethyl, etc.), and then hydrolyzed and condensed to obtain them. Although this method is simple to synthesize and has high efficiency, there are some disadvantages, such as the preparation of disiloxane by hydrolysis and condensation of Si-Cl, HCl will be generated during the hydrolysis process, and the post-treatment will cause environmental pollution, and some functional groups are not suitable for this method. . The latter method is to prepare disiloxanes with active units first, and then further functionalize them to prepare novel disiloxanes. This method is currently widely used, such as 1,3-aminopropyl-1,1,3,3-tetramethyldisiloxane, acryloyloxymethyl or propyldisiloxane, in which acryloyloxy Methyldisiloxane is prepared by reacting 1,3-chloromethyl-1,1,3,3-tetramethyldisiloxane with potassium acrylate under the action of catalyst.
其中，羟烃基二硅氧烷作为一类重要的有机硅产品，用于制备羟烃基封端的聚硅氧烷，是与其它有机聚合物共聚制备特种有机硅共聚物的重要原料之一。但是受限于羟基的反应活性，以羟烃基二硅氧烷为原料制备官能化二硅氧烷的方法主要是通过羟基与异氰酸酯或环氧等少数基团的反应，获得的新型官能化二硅氧烷的种类有限，亟待开发利用羟基的新方法来制备新型官能化二硅氧烷。Among them, hydroxyalkyl disiloxane, as an important class of silicone products, is used to prepare hydroxyalkyl-terminated polysiloxane, and is one of the important raw materials for preparing special silicone copolymers by copolymerization with other organic polymers. However, limited by the reactivity of hydroxyl groups, the method of preparing functionalized disiloxanes from hydroxyhydrocarbyl disiloxanes is mainly through the reaction of hydroxyl groups with isocyanate or epoxy groups to obtain new functionalized disiloxanes. The types of oxanes are limited, and there is an urgent need to develop new methods that utilize hydroxyl groups to prepare novel functionalized disiloxanes.
综上所述，现有技术存在的问题是：In summary, the problems in the prior art are:
水解法产生的酸液对环境危害较大，且处理后废液无法再次利用，且有官能团不适合此方法。而以羟烃基二硅氧烷为原料，通过现有方法合成的二硅氧烷的种类有限，无法获得特殊官能化的二硅氧烷。The acid produced by the hydrolysis method is more harmful to the environment, and the waste liquid after treatment cannot be reused, and the functional group is not suitable for this method. However, using hydroxyalkyl disiloxane as a raw material, the types of disiloxanes synthesized by existing methods are limited, and it is impossible to obtain special functionalized disiloxanes.
发明内容Contents of the invention
针对现有技术存在的缺陷，尤其是现有的水解法产生的酸液对环境危害较大，且处理后废液无法再次利用的问题，以及有官能团不适合此方法，合成二硅氧烷的种类有限，且无法获得特殊官能化的二硅氧烷的不足，本发明提出了一种制备官能化二硅氧烷的新方法。In view of the defects in the existing technology, especially the acid produced by the existing hydrolysis method is more harmful to the environment, and the waste liquid after treatment cannot be reused, and the functional group is not suitable for this method, the method of synthesizing disiloxane Due to the limited types and the inability to obtain special functionalized disiloxanes, the present invention proposes a new method for preparing functionalized disiloxanes.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种官能化二硅氧烷的制备方法，即以羟烃基二硅氧烷和带有吸电子基团的不饱和烯烃，为基础原料，在催化剂的催化下，制备得到具有不同官能化的二硅氧烷。A method for preparing functionalized disiloxanes, that is, using hydroxyhydrocarbyl disiloxanes and unsaturated olefins with electron-withdrawing groups as basic raw materials, under the catalysis of catalysts, to prepare disiloxanes with different functionalizations. silicone.
根据本发明，优选的，为了各物质分散更为均匀，将羟烃基二硅氧烷和带有吸电子基团的不饱和烯烃溶于有机溶剂内进行反应，亦可在无溶剂下进行。According to the present invention, preferably, in order to disperse the various substances more uniformly, the hydroxyhydrocarbyl disiloxane and the unsaturated olefin with an electron-withdrawing group are dissolved in an organic solvent for the reaction, and the reaction can also be carried out without a solvent.
根据本发明，所制备的官能化二硅氧烷的结构式如(Ⅰ)所示，但本发明专利保护范围不仅限于此；According to the present invention, the structural formula of the prepared functionalized disiloxane is shown in (I), but the patent protection scope of the present invention is not limited thereto;
式(Ⅰ)所示结构中，R 1、R 2、R 3、R 4分别独立的选自C 1～C 18的链型烷烃或芳烃；进一步优选的，所述的烷烃选自直链或支链烷烃或环烷烃； In the structure shown in formula (I), R 1 , R 2 , R 3 , and R 4 are independently selected from C 1 -C 18 chain alkanes or aromatic hydrocarbons; further preferably, the alkane is selected from straight chain or Branched chain alkanes or cycloalkanes;
R 5为C 1～C 18的链型烷烃或带杂原子的烷烃或芳烃；进一步优选的，所述的杂原子为O、S、N。R 1、R 2、R 3、R 4、R 5可能相同，也可不同； R 5 is a C 1 -C 18 chain alkane or an alkane or aromatic hydrocarbon with a heteroatom; more preferably, the heteroatom is O, S, N. R 1 , R 2 , R 3 , R 4 , R 5 may be the same or different;
所述的EWG表示吸电子基团；优选的，所述的吸电子基团选自腈基、丙烯酸酯基、砜基、硝基、丙烯酸酯类衍生物的取代基、酰胺基等。The EWG represents an electron-withdrawing group; preferably, the electron-withdrawing group is selected from a nitrile group, an acrylate group, a sulfone group, a nitro group, a substituent of an acrylate derivative, an amide group, and the like.
根据本发明，优选的，所述的带有吸电子基团的不饱和烯烃为双键化合物
R 13为H或R 8，R 8为C 1～C 18的链型烷基或带有O、S等杂原子的烃基，还可以是芳烃基团或环烷烃； R 13 is H or R 8 , and R 8 is a C 1 to C 18 chain alkyl group or a hydrocarbon group with heteroatoms such as O and S, and can also be an aromatic hydrocarbon group or a cycloalkane;
进一步优选的，所述的双键化合物
其中R 6、R 7、R 8为H或C 1～C 18的链型烷基或亦可为带有O、S等杂原子的烃基，还可以是芳烃基团或环烷烃，R 6、R 7、R 8之间可以相同也可不同；R 9、R 10、R 11、R 12是C 1～C 18的链状烷基，亦可为带有O、S等杂原子的烃基，此外还可以是芳烃基团或环烷烃，R 9、R 10、R 11、R 12之间可以相同也可不同；此发明保护范围不仅限于此。 Among them, R 6 , R 7 , R 8 are H or C 1 ~ C 18 chain alkyl groups or hydrocarbon groups with heteroatoms such as O and S, or aromatic hydrocarbon groups or cycloalkanes. R 6 , R 7 and R 8 may be the same or different; R 9 , R 10 , R 11 , and R 12 are C 1 -C 18 chain alkyl groups, or hydrocarbon groups with heteroatoms such as O and S, In addition, it can also be an aromatic hydrocarbon group or a cycloalkane, and R 9 , R 10 , R 11 , and R 12 can be the same or different; the protection scope of this invention is not limited thereto.
根据本发明，优选的，所述的羟烃基二硅氧烷的结构式如式(Ⅱ)所示：According to the present invention, preferably, the structural formula of the hydroxyhydrocarbyl disiloxane is shown in formula (II):
其中，式(Ⅱ)所示结构中，R 1、R 2、R 3、R 4为C 1～C 18的链型烷基或亦可为带有O、S等杂原子的烃基，R 5为C 1～C 18的链型烷基，亦可为带有O、S等杂原子的烃基以及环烷烃和芳烃。R 1、R 2、R 3、R 4、R 5可能相同，也可不同。 Among them, in the structure shown in formula (II), R 1 , R 2 , R 3 , and R 4 are C 1 -C 18 chain alkyl groups or hydrocarbon groups with heteroatoms such as O and S, and R 5 It is a C 1 -C 18 chain alkyl group, and it can also be a hydrocarbon group with heteroatoms such as O and S, as well as cycloalkane and aromatic hydrocarbon. R 1 , R 2 , R 3 , R 4 , and R 5 may be the same or different.
根据本发明，优选的，羟烃基二硅氧烷与带有吸电子基团的不饱和烯烃的摩尔比为1:2～5；According to the present invention, preferably, the molar ratio of hydroxyhydrocarbyl disiloxane to unsaturated olefins with electron-withdrawing groups is 1:2-5;
优选的，催化剂的加入量为反应原料总摩尔量的5mol％～20mol％。Preferably, the catalyst is added in an amount of 5 mol% to 20 mol% of the total molar weight of the reaction raw materials.
根据本发明，优选的，所述的催化剂选自无机碱、有机碱、手性磷酸或金属配合物；According to the present invention, preferably, the catalyst is selected from inorganic bases, organic bases, chiral phosphoric acid or metal complexes;
进一步优选的，所述的无机碱为碳酸钠或碳酸铯；所述的有机碱为4-二甲氨基吡啶、膦腈碱、三苯基膦或叔丁醇钾；所述的金属配合物为三氟甲磺酸镱(Yb(OTf) 3)或金属N-杂环卡宾(NHCs)中的一种或多种混合。 Further preferably, the inorganic base is sodium carbonate or cesium carbonate; the organic base is 4-dimethylaminopyridine, phosphazene base, triphenylphosphine or potassium tert-butoxide; the metal complex is One or more of ytterbium trifluoromethanesulfonate (Yb(OTf) 3 ) or metal N-heterocyclic carbenes (NHCs) are mixed.
根据本发明，优选的，所述的有机溶剂为四氢呋喃、二氯甲烷、乙腈、N,N-二甲基甲酰胺、甲苯、三氯甲烷中的一种或几种混合。According to the present invention, preferably, the organic solvent is one or a mixture of tetrahydrofuran, dichloromethane, acetonitrile, N,N-dimethylformamide, toluene, and chloroform.
根据本发明，优选的，反应温度为20～120℃。According to the present invention, preferably, the reaction temperature is 20-120°C.
根据本发明，优选的，反应时间为0.5～24h。According to the present invention, preferably, the reaction time is 0.5-24 hours.
根据本发明，官能化二硅氧烷的制备方法，一种优选的实施方案，包括步骤如下：According to the present invention, the preparation method of functionalized disiloxane, a preferred embodiment, comprises steps as follows:
将羟烃基二硅氧烷在氩气气氛下加入到三口瓶中，随后相继加入不饱和烯烃、催化剂和有机溶剂，反应在无水无氧条件，20～120℃下进行，反应0.5～24h；反应结束后，稀盐酸或稀碱溶液洗涤反应混合物数次，以除去催化剂，然后用水洗至中性，分出有机相，加入无水硫酸镁或无水硫酸钠干燥，过滤，除去溶剂后粗产物采取蒸馏或者柱色谱纯化，获得目标官能化二硅氧烷。Add hydroxyalkyl disiloxane into a three-neck flask under an argon atmosphere, and then add unsaturated olefin, catalyst and organic solvent successively, and the reaction is carried out under anhydrous and oxygen-free conditions at 20-120°C for 0.5-24 hours; After the reaction, wash the reaction mixture several times with dilute hydrochloric acid or dilute alkali solution to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate or anhydrous sodium sulfate to dry, filter, remove the solvent and then crude The product is purified by distillation or column chromatography to obtain the target functionalized disiloxane.
本发明的反应原理：Reaction principle of the present invention:
该反应是基于羟基—双键发生加成反应，即带有活泼氢的亲核试剂与活性π-体系发生共轭加成反应，该反应体系中亲核受体为氧原子，又称氧杂迈克尔加成，该反应可以高效的提高羟基和双键的利用率，在小分子合成领域有较好的利用。The reaction is based on the hydroxyl-double bond addition reaction, that is, the nucleophile with active hydrogen undergoes a conjugated addition reaction with the active π-system. The nucleophilic acceptor in this reaction system is an oxygen atom, also known as oxa Michael addition, this reaction can efficiently increase the utilization rate of hydroxyl and double bonds, and it is better used in the field of small molecule synthesis.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
本发明官能化二硅氧烷的制备方法简单、反应快速、高效，转化率高，可以获得具有不同官能团的官能化二硅氧烷，为官能化二硅氧烷的制备以及聚硅氧烷的改性提供了有利的方法依据，有较好的进一步的发展前景。The preparation method of the functionalized disiloxane of the present invention is simple, the reaction is fast, efficient, and the conversion rate is high, and the functionalized disiloxane with different functional groups can be obtained, which is the preparation method of the functionalized disiloxane and the preparation of the polysiloxane. The modification provides a favorable method basis and has a good prospect for further development.
图1为实施例1所得目标产物A的核磁氢谱图。Fig. 1 is the NMR spectrum figure of target product A obtained in Example 1.
图2为实施例2所得目标产物B的核磁氢谱图。Fig. 2 is the NMR spectrum of the target product B obtained in Example 2.
图3为实施例3所得目标产物C的核磁氢谱图。Fig. 3 is the NMR spectrum of the target product C obtained in Example 3.
下面结合具体实例对本发明做进一步描述，但本发明保护范围不限于此。The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.
同时下列实施例中所述的实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明均可从商业途径获得。At the same time, the experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials can be obtained from commercial sources unless otherwise specified.
实施例1Example 1
在本实施例中，各物质的用量组成如下：1,3-羟丙基-1,1,3,3-四甲基二硅氧烷0.5g，丙烯腈0.212g，催化剂膦腈碱t-BuP 20.0735g，四氢呋喃10mL，在氩气气氛下将相应的1,3-羟丙基-1,1,3,3-四甲基二硅氧烷、丙烯腈和催化剂依次加入到经过三次冻融泵循环过的三口瓶内，无水无氧条件下室温搅拌4h，稀盐酸洗涤反应混合物数次，以除去催化剂，然后用水洗至中性，分出有机相，加入无水硫酸镁干燥，过滤，旋蒸除去有机溶剂，所得产物即为目标官能化二硅氧烷A。 In this example, the dosage of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.212 g of acrylonitrile, catalyst phosphazene base t- BuP 2 0.0735g, tetrahydrofuran 10mL, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were added to the In the three-neck flask that has been circulated by the melting pump, stir at room temperature for 4 hours under anhydrous and anaerobic conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, Filtration, rotary evaporation to remove the organic solvent, and the obtained product is the target functionalized disiloxane A.
实施例2Example 2
在本实施例中，各物质的用量组成如下：1,3-羟丙基-1,1,3,3-四甲基二硅氧烷0.5g，甲基乙烯基砜0.4246g，催化剂4-二甲氨基吡啶0.0732g，在氩气气氛下将相应的1,3-羟丙基-1,1,3,3-四甲基二硅氧烷、甲基乙烯基砜和催化剂依次加入到经过三次冻融泵循环过的三口瓶内，无水无氧条件下80℃搅拌12h，稀盐酸洗涤反应混合物数次，以除去催化剂，然后用水洗至中性，分出有机相，加入无水硫酸镁干燥，过滤，旋蒸除去有机溶剂，柱色谱纯化，所得产物即为目标官能化二硅氧烷B。In this example, the composition of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.4246 g of methyl vinyl sulfone, and 4- Dimethylaminopyridine 0.0732g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, methyl vinyl sulfone and catalyst were added to the In the three-neck flask that has been circulated by the freeze-thaw pump three times, stir at 80°C for 12 hours under anhydrous and oxygen-free conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, and add anhydrous sulfuric acid Dried over magnesium, filtered, rotary evaporated to remove the organic solvent, purified by column chromatography, and the obtained product was the target functionalized disiloxane B.
实施例3Example 3
在本实施例中，各物质的用量组成如下：1,3-羟丙基-1,1,3,3-四甲基二硅氧烷0.5g，苯基乙烯基砜0.6728g，催化剂4-二甲氨基吡啶0.0488g，在氩气气氛下将相应的1,3-羟丙基-1,1,3,3-四甲基二硅氧烷、丙烯腈和催化剂依次加入到经过三次冻融泵循环过的三口瓶内，无水无氧条件下室温搅拌4h，稀盐酸洗涤反应混合物数次，以除去催化剂，然后用水洗至中性，分出有机相，加入无水硫酸镁干燥，过滤，旋蒸除去有机溶剂，柱色谱纯化，所得产物即为目标官能化二硅氧烷C。In this example, the dosage of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.6728 g of phenyl vinyl sulfone, and 4- Dimethylaminopyridine 0.0488g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were successively added to the In the three-neck flask that has been circulated by the pump, stir at room temperature for 4 hours under anhydrous and oxygen-free conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, filter , the organic solvent was removed by rotary evaporation, and purified by column chromatography, the obtained product was the target functionalized disiloxane C.
实施例4Example 4
在本实施例中，各物质的用量组成如下：1,3-羟丙基-1,1,3,3-四甲基二硅氧烷0.5g，丙烯酸乙酯0.4g，催化剂4-二甲氨基吡啶0.0732g，在氩气气氛下将相应的1,3-羟丙基-1,1,3,3-四甲基二硅氧烷、丙烯腈和催化剂依次加入到经过三次冻融泵循环过的三口瓶内，无水无氧条件下室温搅拌4h，稀盐酸洗涤反应混合物数次，以除去催化剂，然后用水洗至中性，分出有机相，加入无水硫酸镁干燥，过滤，旋蒸除去有机溶剂，柱色谱纯化，所得产物即为目标官能化二硅氧烷。In this example, the composition of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.4 g of ethyl acrylate, catalyst 4-dimethyl Aminopyridine 0.0732g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were sequentially added to the mixture after three freeze-thaw pump cycles In the three-neck flask that has been passed, stir at room temperature for 4 hours under anhydrous and oxygen-free conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, filter, spin The organic solvent was evaporated and purified by column chromatography, and the obtained product was the target functionalized disiloxane.
实施例5Example 5
在本实施例中，各物质的用量组成如下：1,3-羟丙基-1,1,3,3-四甲基二硅氧烷0.5g，N,N-二甲基丙烯酰胺0.396g，叔丁醇钾0.0224g，在氩气气氛下将相应的1,3-羟丙基-1,1,3,3-四甲基二硅氧烷、丙烯腈和催化剂依次加入到经过三次冻融泵循环过的三口瓶内，无水无氧条件下室温搅拌4h，稀盐酸洗涤反应混合物数次，以除去催化剂，然后用水洗至中性，分出有机相，加入无水硫酸镁干燥，过滤，旋蒸除去有机溶剂，柱色谱纯化，所得产物即为目标官能化二硅氧烷。In this example, the dosage of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.396 g of N,N-dimethylacrylamide , Potassium tert-butoxide 0.0224g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were sequentially added to the In the three-neck flask that has been circulated by the melting pump, stir at room temperature for 4 hours under anhydrous and anaerobic conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, Filtration, rotary evaporation to remove the organic solvent, and column chromatography purification, the obtained product is the target functionalized disiloxane.
实施例6Example 6
在本实施例中，各物质的用量组成如下：1,3-羟丙基-1,1,3,3-四甲基二硅氧烷0.5g，乙 烯基磷酸二乙酯0.657g，催化剂膦腈碱t-BuP2 0.0735g，在氩气气氛下将相应的1,3-羟丙基-1,1,3,3-四甲基二硅氧烷、丙烯腈和催化剂依次加入到经过三次冻融泵循环过的三口瓶内，无水无氧条件下室温搅拌4h，稀盐酸洗涤反应混合物数次，以除去催化剂，然后用水洗至中性，分出有机相，加入无水硫酸镁干燥，过滤，旋蒸除去有机溶剂，柱色谱纯化，所得产物即为目标官能化二硅氧烷。In this example, the composition of each substance is as follows: 0.5 g of 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, 0.657 g of vinyl phosphate diethyl ester, catalyst phosphine Nitrile base t-BuP2 0.0735g, under argon atmosphere, the corresponding 1,3-hydroxypropyl-1,1,3,3-tetramethyldisiloxane, acrylonitrile and catalyst were added successively to the In the three-neck flask that has been circulated by the melting pump, stir at room temperature for 4 hours under anhydrous and oxygen-free conditions, wash the reaction mixture several times with dilute hydrochloric acid to remove the catalyst, then wash with water until neutral, separate the organic phase, add anhydrous magnesium sulfate to dry, Filtration, rotary evaporation to remove the organic solvent, and column chromatography purification, the obtained product is the target functionalized disiloxane.
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