CN109970572B - Synthetic method of double-bond end-capping compound - Google Patents
Synthetic method of double-bond end-capping compound Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
Abstract
The invention provides a synthetic method of a double-bond end-capped compound, which comprises the following steps: 1) taking a compound with a group containing active hydrogen on a primary carbon and/or a secondary carbon as a substrate, carrying out contact reaction on the substrate and epoxy isobutane to carry out tertiary alcohol end capping to obtain a tertiary alcohol end capping product; 2) and (3) carrying out intramolecular dehydration on the tertiary alcohol end-capped product under the action of a Lewis acid catalyst to obtain a double-bond end-capped product. The synthesis method can improve the double bond end-capping rate, and the synthesis process is simple and controllable, and is green and environment-friendly.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing a double-bond end-capping compound.
Background
The double-bond end-capping compound can be used in the synthesis and application fields of unsaturated polyester, unsaturated polyether, polyether amine, modification of the unsaturated polyester, unsaturated polyether, polyether amine, grafting epoxidation and the like. Such as higher organic reaction intermediates for carbon chain extension, polyurethane foaming silicone oil, double bond end-capping modification of surfactant fatty alcohol, fluorosilicone modified polymer precursors, and the like. The application fields thereof are, for example: can be used for preparing medical intermediates, epoxy resin, polymer alloys such as epoxy resin/polyurethane/polyacrylate and the like, IPN, light-cured resin, modified resin (silicon modification, fluorine modification and the like), graft type surfactant and the like.
The synthetic method of double bond end capping is applied to medical intermediates, and mainly can solve the problem that the electron-withdrawing capability of the carbon at the ortho position of hydroxyl is weak in the conventional elimination process. The polyether amine can be prepared by adopting an amine alkene addition mode to be used as an epoxy resin monomer or a cross-linking agent when the epoxy resin is applied to epoxy resin. The modified cross-linking agent is applied to polymer alloys, IPNs and the like, can design molecules, intentionally improves the degree of freedom between cross-linking points or staggered points, improves the cross-linking density, simultaneously improves the toughness and solves the problem of brittleness. The application in the photocuring resin industry can adopt polyhydroxy compounds with higher functionality and a polyene end capping mode to obtain the reactive diluent containing double bonds with higher functionality. Meanwhile, the polyurethane-modified polyurethane adhesive is different from polyurethane reaction, and a carbamate bond is not introduced, so that the viscosity of the diluent is low, and the leveling property is good; the method is applied to the modified resin industry, and a series of differentiated modified resins are obtained by carrying out addition of silicon hydride, fluorine hydride, acid alkene and the like on unsaturated double bonds. The method is applied to the synthesis of the surfactant, adopts substrates such as high-carbon alcohol or polyether and the like to carry out double-bond end capping, and then accesses the substrate with opposite surface tension to the unsaturated site with reaction activity, and can be popularized as a special synthesis method.
Currently, the commonly used method for blocking double bonds is to perform esterification (transesterification) or etherification to block end ester groups or ether groups (Williamson reaction) on polyether or other polyhydroxy compounds.
CN99124993.3 describes a preparation method of trimethylolpropane allyl ether, which adopts Williamson reaction, firstly alcoholizes, etherifies with allyl halide containing unsaturated groups, and purifies the product to obtain the trimethylolpropane allyl ether. The preparation method is complex, the product is difficult to purify and crystallize, the color number is high, and the end-capping rate is low.
CN105061750A, CN104262612A, CN200810172443.3 and the like describe a synthesis method of an ester-terminated polycarboxylic acid water reducing agent. The polyether monol reacts with a compound containing double bonds and isocyanate groups to insert the double bonds into the polyether, or the polyether reacts with carboxylic acid through esterification, so that the polyether is used for the water reducing agent and has the characteristics of low mixing amount, high water reducing rate, good slump retaining property, excellent dispersing performance and the like. However, because the method of introducing double bonds into polyether introduces urethane bonds into the system, the viscosity of the system is relatively high, the workability is poor, and the bonding force of the synthesized adhesive to a low-polarity interface is reduced due to the action of strong hydrogen bonds.
CN200910052766.3 discloses a method for synthesizing end-capped unsaturated polyester resin, which mainly adopts unsaturated anhydride to react with active hydrogen to esterify and obtain double-bond end-capped polyester or polyether products. However, the hydroxyl reacts with the acid anhydride to generate carboxyl, which affects the performance of the final product.
CN201210526464.7, CN101982481A, CN102358779A, US4510048, etc. mention the use of etherification reactions to end-cap saturated polyethers with unsaturated hydrocarbon groups or to end-cap unsaturated polyethers with alkyl groups. Most of them are prepared by salifying polyether with alkali metalating agent (such as sodium methoxide, potassium methoxide solid or alcoholic solution, sodium hydroxide or potassium hydroxide solid or aqueous solution, etc.), and then Williamson reacting with halogenated alkane, halogenated alkene or alkyl sulfate. In the process of alcohol salinization reaction, the used alkali metallization reagent can generate destructive effect on double bonds of raw material polyether at high temperature, while in the preparation of high-quality polyether modified organic silicon, the silicon-hydrogen addition reaction of end-capped unsaturated polyether and hydrogen-containing silicone oil is involved, the higher the content of polyether double bonds is, the faster the reaction speed is, and the better the performance of the prepared organic silicon is; on the contrary, when the terminated unsaturated polyether with low double bond content is adopted to carry out hydrosilylation, not only is terminated polyether impurities with damaged double bonds introduced, but also the reaction speed and the product performance are influenced.
The two methods have the common point that a double bond is introduced into a substrate with a certain group by adopting an equilibrium reaction mode, the defects of the equilibrium reaction mode are that the reversibility is strong, the reaction conversion rate of most reactions is low, the actual end capping rate of the obtained product is low (directly causing the reduction and instability of the product quality) or more energy consumption is needed to reach the required end capping rate, and therefore the synthesis cost is improved.
Disclosure of Invention
Compared with the conventional double-bond end-capping synthesis method, the synthesis method disclosed by the invention can improve the double-bond end-capping rate, and is simple and controllable in synthesis process, green and environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a synthetic method of a double-bond end-capped compound, which comprises the following steps:
1) taking a compound with a group containing active hydrogen on a primary carbon and/or a secondary carbon as a substrate, carrying out contact reaction on the substrate and epoxy isobutane to carry out tertiary alcohol end capping to obtain a tertiary alcohol end capping product;
2) under the action of Lewis acid catalyst, tertiary alcohol groups of the tertiary alcohol end-capped product are subjected to intramolecular dehydration to obtain a double-bond end-capped product, namely, hydroxyl on terminal tertiary carbon is removed to form terminal alkenyl end capping.
In the synthesis method of the invention, the active hydrogen-containing group can be one or more. Preferably, the active hydrogen-containing group is one or more of a primary amine group, a secondary amine group, a primary hydroxyl group and a secondary hydroxyl group. Preferably, the sum of the number of both primary and secondary amino groups, m, is from 0 to 6, the sum of the number of both primary and secondary hydroxyl groups, n, is from 0 to 6, and m + n > 0.
The synthesis method of the present invention preferably further comprises, before the reaction in step 1), the following steps: the substrate used for the reaction with the epoxyisobutane was deprived of water to avoid side reactions of water and IBO. In one embodiment, the removal of water can be carried out in particular by distillation under reduced pressure.
In the synthesis method of the present invention, preferably, when the active hydrogen-containing group includes at least one of a primary hydroxyl group or a secondary hydroxyl group, before the step of removing water from the substrate, in order to promote the tertiary alcohol capping reaction in the subsequent step 1), the method further includes the following steps: contacting the substrate with a basic catalyst. Preferably, the contacting of the substrate and the basic catalyst is carried out under a nitrogen atmosphere, which may be obtained, for example, by nitrogen displacement; for better promotion of the tertiary alcohol end capping, the contacting is carried out at a temperature of 80 to 120 ℃; preferred pressure conditions are-0.09 to-0.1 MPa, for example-0.095 to-0.1 MPa; the preferred contact time is 1-3 h; preferably, the dosage of the alkaline catalyst is 0.1-1% of the mass of the substrate, and the dosage is preferably the dosage, so that the reaction is easy to control and the side reaction is less; too much amount is used, the controllability of the reaction is poor, side reactions are increased, and a typical side reaction is the hydrolysis of ether bonds.
In the synthesis method of the present invention, preferably, the basic catalyst is selected from one or more of alkali metal hydroxide and alkali metal alkoxide, preferably one or more of sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide, and the preferred catalyst has wide sources and economic price, and is suitable for industrial scale-up production. The synthesis method of the present invention preferably further comprises, after step 2), the following steps: to the resulting double bond-terminated product is added a neutralizing agent (e.g., sulfuric acid, phosphoric acid, and the like, which are conventional in the art) to neutralize the basic catalyst. Preferably, when the substrate is a compound having a polyether structure, the product obtained by the neutralization contains 0.2 to 1 wt% of alkali metal ions derived from a catalyst and having a function of protecting ether bonds from being broken in the dehydration reaction.
According to the synthesis method, the preferable molar ratio of epoxy isobutane to the active hydrogen in the substrate is 1: 1-1.5: 1.
in the synthesis method of the invention, preferably, the reaction temperature in the step 1) is 100-150 ℃; the preferable reaction pressure is 0.05-0.5 MPa; preferably, the reaction time is 1 to 10 hours.
In the synthesis method of the present invention, preferably, in step 2), the lewis acid catalyst is a solid heterogeneous catalyst. Preferably, the lewis acid catalyst is selected from one or more of aluminum halide, iron halide, zinc halide, boron halide, aluminum oxide, iron oxide and zinc oxide, and the preferred catalyst has the advantages of easy preparation, high yield, abundant sources, economical price and the like. The solid heterogeneous lewis acid catalyst may specifically be a commercially available raw material, or may be obtained by self-preparation, for example, by a precipitation roasting method, and the specific preparation process thereof is prior art in the field and is not described in detail herein; for example, the following steps can be performed: the Lewis acid salts (such as iron halide, aluminum oxide and the like) are dispersed in a solvent (such as DMF and the like), the catalyst is precipitated by evaporating the solvent, and is filtered and dried after standing and depositing, and is roasted in a muffle furnace at the temperature of more than 400 ℃ until trace amount of the solvent is remained, and the catalyst can be filled for standby (the solid heterogeneous catalyst used in the embodiment is prepared by the method and is not repeated).
In the synthesis method, the specific surface area of the solid heterogeneous catalyst is preferably less than or equal to 2000m2A concentration of 300 to 1500m2(ii) in terms of/g. The inventor of the application finds that the specific surface area is less than or equal to 2000m2A specific volume of 300 to 1500m2The solid heterogeneous Lewis acid catalyst can avoid the problem of catalyst blockage caused by contacting a large amount of high-viscosity substrates (such as a polyether system), the service life of the catalyst reaches over 5000h, the regeneration efficiency of the catalyst is higher than 90 percent, and the production cost is greatly saved.
In the synthesis method, preferably, the reaction in the step 2) is carried out in a fixed bed, and the reaction temperature is 80-150 ℃; the preferable mass space velocity is 0.5-10 h-1(ii) a The reaction is carried out in a fixed bed, preferably with the solid heterogeneous Lewis acid catalysts described above.
The synthesis method of the present invention preferably further comprises the following steps after step 2): purifying the prepared double-bond end-capping product; the specific operation of purification can adopt the conventional purification means existing in the field, and the purification includes but is not limited to one or more of filtration, adsorption, water removal, rectification, crystallization, extraction or reduced pressure distillation, and the purposes of decolorization, metal ion removal and the like are achieved. The adsorption may be performed by using silicate adsorbent, such as magnesium silicate and aluminum silicate.
The synthesis method of the present invention is suitable for compounds having active hydrogen groups on primary and/or secondary carbons, including but not limited to one or more of alkyl amines, alkyl polyamines, alkyl alcohol amines, alkyl alcohols, alkyl polyols, etc., wherein "alkyl polyamines" refers to alkyl diamines and above, and "alkyl polyols" refers to alkyl diols and above. The substrate may specifically be, but is not limited to, one or more of ethylenediamine, trimethylolpropane, ethanolamine, pentaerythritol, sorbitol, methanol, ethylamine, and the like.
The technical scheme provided by the invention has the following beneficial effects:
the invention adopts IBO (epoxy isobutane) as a blocking agent to replace systems such as allyl halogenated hydrocarbon and the like, and the IBO and a substrate with an active hydrogen-containing group on secondary carbon and/or primary carbon participate in anionic polymerization reaction similar to polyether. Has the advantages that: 1) the synthesis process is simple and controllable, the yield is high, and the end-capping rate can reach more than 99 percent; the synthesis process is stable; 2) the byproduct is water, no organic byproduct is generated, and the process is green and environment-friendly; 3) the substrate range is wide, the compound with active hydrogen groups on primary carbon and/or secondary carbon can be suitable for use, and the product differentiation degree is high.
The invention mainly terminates the end by introducing tertiary alcohol group, thereby eliminating dehydration in the molecule, having high double bond terminating rate and reducing the cost.
The double-bond end-capped product prepared by the method can be used for preparing unsaturated polyester and unsaturated polyether, for example, the double-bond end-capped product can be used for preparing mono-functional or multi-functional unsaturated double-bond end-capped polyester/polyether with the molecular weight of 1000-10000, so that the flexibility of a cross-linked network of the polyester/polyether is improved; the method can also be used for preparing polyether amine, and amino-terminated polyether is easily obtained by adding hydrogenated amine alkene on the basis of unsaturated polyether; and can also be used in the synthesis and application fields of modification (such as graft polyether and polyester containing hydrosilane, hydrofluoric acid, hydrosilicane oil and the like), graft epoxidation (such as unsaturated double bond oxidation by hydrogen peroxide, tertiary butanol peroxide and the like to synthesize epoxy polyether polyester resin containing epoxy groups), and the like.
Compared with the conventional esterification method and Williamson etherification method, the synthesis method provided by the invention has the advantages of mild reaction conditions, high double bond end-capping rate, high product yield, few byproducts, short production period and the like, and is suitable for industrial amplification.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The test methods referred to in the examples include pH test, hydroxyl value test, acid value test, sodium and potassium determination, water content determination and unsaturation test. Wherein the pH test was performed using a benchtop pH meter model mettler-toledo S400. Hydroxyl value test the hydroxyl value test was carried out with reference to GB/T12008.3-2009 Plastic polyether polyol part 3 determination of hydroxyl value. Acid number test the test was carried out with reference to the determination of the acid number of part 5 of the GB/T12008.5-2010 plastic polyether polyol. Unsaturation the tests were carried out with reference to GB/T12008.6-2010 Plastic polyether polyol part 6 determination of unsaturation. Sodium potassium ion tests were tested with reference to GB/T12008.4-2009 Plastic polyether polyol part 4. determination of sodium and potassium. Water content testing the test was carried out with reference to the determination of the water content of the polyols used in polyurethane production from GB/T22313-2008 plastic.
All the products mentioned in the examples were purified and tested for unsaturation, which was used to back-calculate the overall process yield, e.g., 1mol double bond in 1mol starting material with 1 functionality (e.g., methanol) and 100% endcapping.
The reagents used in the examples were all from the reagent avastin, analytically pure.
The present invention will be described in detail with reference to the following examples; the scope of the invention is not limited thereto.
Example 1
The substrate in this example was ethylenediamine.
The preparation of the double bond end-capping compound was carried out by the following steps:
1) in a three-necked 1000ml flask with stirring, a thermometer and a nitrogen atmosphere, 120g of ethylenediamine (substrate) was first added to the reaction vessel;
adding 576g (the molar ratio of active hydrogen in the substrate is 1: 1) epoxy Isobutane (IBO), and carrying out tertiary alcohol end capping for 1h at the reaction temperature of 100 ℃ and the reaction pressure of 0.15 MPa; the theoretical hydroxyl value of the product is 644.83mgKOH/g, the measured value of the hydroxyl value of the tertiary alcohol end-capped product prepared in the step is 644.8mgKOH/g, and the in-situ conversion is basically achieved.
2) The intermediate (tertiary alcohol-terminated product) prepared from step 1) took 0.5h-1The mass airspeed is passed through a fixed bed (filled with a solid heterogeneous catalyst) with a reaction temperature of 80 ℃, intramolecular dehydration and dehydration purification are carried out, and a double-bond end-capped product is obtained:
the solid heterogeneous catalyst used in this step is prepared from AlCl370 wt% and Fe2O330 wt% of the catalyst, and the specific surface area of the catalyst is 300m2/g。
3) Purifying the end-capped crude product obtained in the step 2).
Through detection, the unsaturation degree of the purified product is 14.056mmol/g, the double bond end capping rate of the converted product is 99.8%, and other indexes of the product are qualified through detection (the water content is less than or equal to 0.05 wt%, the acid value is less than or equal to 0.1mgKOH/g, and the pH value is 5-7). The solid heterogeneous catalyst used in the embodiment is used for more than 5000h, and the double bond capping rate of the product still reaches more than 99%.
Example 2
The substrate of this example was trimethylolpropane.
The preparation of the double bond end-capping compound was carried out by the following steps:
1) in a three-necked 1000ml flask with stirring, a thermometer and a nitrogen atmosphere, 268g trimethylolpropane (substrate) was added to a reaction vessel, 0.536g (0.2% by mass of the substrate) sodium methoxide was added, and the mixture was contacted at a reaction temperature of 120 ℃ and a pressure of-0.097 MPa for 2 hours, and dehydrated under reduced pressure;
adding 648g (mole ratio of IBO to active hydrogen in substrate is 1.5: 1) epoxy Isobutane (IBO), and carrying out tertiary alcohol end capping for 10h at reaction temperature of 150 ℃ and reaction pressure of 0.2 MPa;
the theoretical hydroxyl value of the product is 500.89mgKOH/g, the measured value of the hydroxyl value of the tertiary alcohol end-capped product prepared in the step is 501mgKOH/g, and the in-situ conversion is basically achieved.
2) The intermediate (tertiary alcohol-terminated product) prepared from step 1) took 10h-1The mass space velocity passes through a fixed bed (filled with a solid heterogeneous catalyst) with the reaction temperature of 150 ℃, intramolecular dehydration is carried out, and dehydration and purification are carried out to obtain a double-bond end-capped product. The solid heterogeneous catalyst is prepared from ZnCl250 wt% and Al2O350 wt% of the catalyst, the specific surface area of the catalyst is 1150m2/g。
3) Neutralizing the end-capped crude product obtained in the step 2) by using phosphoric acid, wherein the content of alkali metal ions in a system is 0.2%, and then adsorbing by using a silicate adsorbent (magnesium silicate) and purifying.
Through detection, the unsaturation degree of the purified product is 9.844mmol/g, the double bond end capping rate of the converted product is 99.1%, and other indexes of the product are qualified through detection (the water content is less than or equal to 0.05 wt%, the acid value is less than or equal to 0.1mgKOH/g, and the pH value is 5-7). The solid heterogeneous catalyst used in the embodiment is used for more than 5000h, and the double bond capping rate of the product still reaches more than 99%.
Example 3
The substrate in this example was ethanolamine.
The preparation of the double bond end-capping compound was carried out by the following steps:
1) in a three-neck 1000ml flask with stirring, a thermometer and a nitrogen atmosphere, 184g ethanolamine (substrate) is firstly added into a reaction vessel, 0.18g (0.1 percent of the substrate mass) of sodium hydroxide is added, the mixture is contacted for 3 hours at the reaction temperature of 100 ℃ and the pressure of-0.1 MPa, and the pressure is reduced for dehydration;
adding 345.6g (the molar ratio of IBO to active hydrogen in a substrate is 1.2: 1) epoxy Isobutane (IBO), and carrying out tertiary alcohol end capping for 7 hours at the reaction temperature of 125 ℃ and the reaction pressure of 0.4 MPa;
the theoretical hydroxyl value of the product is 578.35mgKOH/g, the measured value of the hydroxyl value of the tertiary alcohol end capping product prepared in the step is 578.4mgKOH/g, and the in-situ conversion is basically achieved.
2) The intermediate (tertiary alcohol-terminated product) prepared from step 1) took 5h-1The mass space velocity passes through a fixed bed (filled with a solid heterogeneous catalyst) with the reaction temperature of 120 ℃, intramolecular dehydration is carried out, and dehydration and purification are carried out to obtain a double-bond end-capped product. The solid heterogeneous catalyst adopts BF340 wt% and ZnO 60 wt%, and the specific surface area of the catalyst is 2000m2/g。
3) Neutralizing the end-capped crude product obtained in the step 2) with phosphoric acid, wherein the content of alkali metal ions in the system is 0.1%, and then purifying the product.
Through detection, the unsaturation degree of the purified product is 9.794mmol/g, the double bond end capping rate of the converted product is 99.9%, and other indexes of the product are qualified through detection (the water content is less than or equal to 0.05 wt%, the acid value is less than or equal to 0.1mgKOH/g, and the pH value is 5-7). The solid heterogeneous catalyst used in the embodiment is used for more than 5000h, and the double bond capping rate of the product still reaches more than 99%.
Example 4
The substrate in this example was pentaerythritol.
The preparation of the double bond end-capping compound was carried out by the following steps:
1) in a three-neck 1000ml flask with stirring, thermometer and nitrogen atmosphere, firstly 136g of pentaerythritol (substrate) is added into a reaction vessel, 1.36g (1 percent of the substrate mass) of potassium methoxide is added, the mixture is contacted for 1h at the reaction temperature of 90 ℃ and the pressure of-0.095 MPa, and the mixture is decompressed and dehydrated;
adding 374g (the molar ratio of IBO to active hydrogen in a substrate is 1.3: 1) of epoxy Isobutane (IBO), and carrying out tertiary alcohol end capping for 5 hours at the reaction temperature of 110 ℃ and the reaction pressure of 0.3 MPa;
the theoretical hydroxyl value of the product is 529.24mgKOH/g, the measured value of the hydroxyl value of the tertiary alcohol end-capped product prepared in the step is 529mgKOH/g, and the in-situ conversion is basically achieved.
2) The intermediate (tertiary alcohol-terminated product) prepared from step 1) took 8h-1The mass space velocity was passed through a fixed bed (packed with solid heterogeneous catalyst) at a reaction temperature of 130 c,intramolecular dehydration and dehydration purification are carried out to obtain a double-bond end-capped product. The solid heterogeneous catalyst is prepared from FeBr330 wt% of Fe and2O370 wt% of the catalyst, and the specific surface area of the catalyst is 300m2/g。
3) Neutralizing the end-capped crude product obtained in the step 2) with phosphoric acid, wherein the content of alkali metal ions in a system is 1%, and then purifying the product.
Through detection, the unsaturation degree of the purified product is 11.011mmol/g, the double bond end capping rate of the converted product is 99.1%, and other indexes of the product are qualified through detection (the water content is less than or equal to 0.05 wt%, the acid value is less than or equal to 0.1mgKOH/g, and the pH value is 5-7). The solid heterogeneous catalyst used in the embodiment is used for more than 5000h, and the double bond capping rate of the product still reaches more than 99%.
Example 5
The substrate in this example was sorbitol.
The preparation of the double bond end-capping compound was carried out by the following steps:
according to the synthesis method, the following steps are adopted for reaction:
1) in a three-neck 1000ml flask with stirring, a thermometer and a nitrogen atmosphere, 182g of sorbitol (substrate) is firstly added into a reaction vessel, 0.91g (0.5 percent of the mass of the substrate) of potassium hydroxide is added, the mixture is contacted for 2 hours at the reaction temperature of 110 ℃ and the pressure of-0.098 MPa, and the pressure is reduced for dehydration;
adding 432g (the molar ratio of IBO to active hydrogen in a substrate is 1.2: 1) epoxy Isobutane (IBO), and carrying out tertiary alcohol end capping for 1h at the reaction temperature of 100 ℃ and the reaction pressure of 0.1 MPa;
the theoretical hydroxyl value of the product is 548.21mgKOH/g, the measured value of the hydroxyl value of the tertiary alcohol end-capped product prepared in the step is 548mgKOH/g, and the in-situ conversion is basically achieved.
2) The intermediate (tertiary alcohol-terminated product) prepared from step 1) took 3h-1The mass space velocity is passed through a fixed bed (filled with solid heterogeneous catalyst) with the reaction temperature of 100 ℃, intramolecular dehydration is carried out, and dehydration purification is carried out to obtain a double-bond end-capped product. The solid heterogeneous catalyst consists of Al2O3Prepared separately, specific surface area 2000m2/g。
3) Neutralizing the end-capped crude product obtained in the step 2) with phosphoric acid, wherein the content of alkali metal ions in a system is 0.5%, and then purifying the product.
Through detection, the unsaturation degree of the purified product is 10.768mmol/g, the double bond end capping rate of the converted product is 99.5%, and other indexes of the product are qualified through detection (the water content is less than or equal to 0.05 wt%, the acid value is less than or equal to 0.1mgKOH/g, and the pH value is 5-7). The solid heterogeneous catalyst used in the embodiment is used for more than 5000h, and the double bond capping rate of the product still reaches more than 99%.
Example 6
The substrate in this example was methanol.
The preparation of the double bond end-capping compound was carried out by the following steps:
1) in a three-neck 1000ml flask with a stirring, thermometer and nitrogen atmosphere, 160g of methanol (substrate) is firstly added into a reaction vessel, 0.48g (0.3 percent of the substrate mass) of sodium hydroxide is added, the mixture is contacted for 3 hours at the reaction temperature of 120 ℃ and the pressure of-0.095 MPa, and the pressure is reduced for dehydration;
adding 360g (the molar ratio of IBO to active hydrogen in a substrate is 1: 1) of epoxy Isobutane (IBO), and carrying out tertiary alcohol end capping for 10 hours at the reaction temperature of 130 ℃ and the reaction pressure of 0.5 MPa;
the theoretical hydroxyl value of the product is 539.42mgKOH/g, the measured value of the hydroxyl value of the tertiary alcohol end-capped product prepared in the step is 538mgKOH/g, and the in-situ conversion is basically achieved.
2) The intermediate (tertiary alcohol-terminated product) prepared from step 1) was used for 1h-1The mass space velocity is passed through a fixed bed (filled with solid heterogeneous catalyst) with the reaction temperature of 95 ℃ to carry out intramolecular dehydration, dehydration and purification, thus obtaining the double-bond end-capped product. The solid heterogeneous catalyst used in the step is ZnCl230 wt% and Al2O370 wt% of the catalyst, and the specific surface area of the catalyst is 1700m2/g。
3) Neutralizing the end-capped crude product obtained in the step 2) with phosphoric acid, wherein the content of alkali metal ions in the system is 0.3%, and then purifying the product.
Through detection, the unsaturation degree of the purified product is 11.352mmol/g, the double bond end capping rate of the converted product is 99.9%, and other indexes of the product are qualified through detection (the water content is less than or equal to 0.05 wt%, the acid value is less than or equal to 0.1mgKOH/g, and the pH value is 5-7). The solid heterogeneous catalyst used in the embodiment is used for more than 5000h, and the double bond capping rate of the product still reaches more than 99%.
Example 7
The substrate in this example was ethylamine.
According to the synthesis method, the following steps are adopted for reaction:
1) in a three-mouth 1000ml flask with stirring, a thermometer and a nitrogen atmosphere, firstly adding 180g of ethylamine (substrate) into a reaction vessel, and dehydrating under reduced pressure for 1h at the reaction temperature of 80 ℃ and the pressure of-0.1 MPa;
adding 432g (the molar ratio of IBO to active hydrogen in a substrate is 1.5: 1) epoxy Isobutane (IBO), and carrying out tertiary alcohol end capping for 3 hours at the reaction temperature of 140 ℃ and the reaction pressure of 0.05 MPa;
the theoretical hydroxyl value of the product is 593.65mgKOH/g, the hydroxyl value of the tertiary alcohol end capping product prepared in the step is measured to be 593.65mgKOH/g, and the in-situ conversion is basically achieved.
2) The intermediate (tertiary alcohol-terminated product) prepared from step 1) took 2.5h-1The mass space velocity passes through a fixed bed (filled with a solid heterogeneous catalyst) with the reaction temperature of 140 ℃, and intramolecular dehydration, dehydration and purification are carried out to obtain a double-bond end-capped product. The fixed bed catalyst used in the step adopts AlCl350 wt% and Fe2O350 wt% of the catalyst, and the specific surface area of the catalyst is 1800m2/g。
3) Purifying the end-capped crude product obtained in the step 2).
Through detection, the unsaturation degree of the purified product is 9.891mmol/g, the double bond end capping rate of the converted product is 99.9%, and other indexes of the product are qualified through detection (the water content is less than or equal to 0.05 wt%, the acid value is less than or equal to 0.1mgKOH/g, and the pH value is 5-7). The solid heterogeneous catalyst used in the embodiment is used for more than 5000h, and the double bond capping rate of the product still reaches more than 99%.
Example 8
This example is substantially the same as example 1, except that a solid heterogeneous catalyst with a high specific surface area (comparative surface) is used in step 2)Product of 5000m2And/g), when the service time of the catalyst is less than 1000h, the activity of the catalyst can also reach more than 99 percent, but the catalyst is subjected to a large amount of catalyst blockage and coking after being recycled for more than 1000h, the efficiency of the catalyst is greatly reduced, and the catalyst does not meet the industrial amplification requirement.
Comparative example 1
The synthesis of the product in this comparative example is the existing Williamson reaction (this reaction is only applicable to hydroxyl-terminated substrates):
after alkaline metal salt (potassium hydroxide) is added to carry out alcoholization on a substrate (methanol) by equimolar alkaline metal salt (molar ratio is 1: 1), a halogenated allyl raw material (3-chloropropene) is added to react with the substrate according to the molar ratio of 1:1 at the temperature of 150 ℃ and under the pressure of 0.1-0.5MPa, and the prepared product has the double bond end capping rate of less than 87 percent and the end capping rate reported in documents and patents as 95 percent at most which is far lower than the product performance in the embodiment example of the invention.
Comparative example 2
This comparative example is substantially the same as comparative example 1 except that the molar ratio of the alkali metal salt to the substrate added is 3:1 (excess) and the molar ratio of the haloallylic starting material to the substrate added is 5: 1. The double bond end capping rate of the obtained product is less than 87 percent.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (13)
1. A synthetic method of a double-bond end-capping compound is characterized by comprising the following steps:
1) taking a compound with a group containing active hydrogen on a primary carbon and/or a secondary carbon as a substrate, carrying out contact reaction on the substrate and epoxy isobutane to carry out tertiary alcohol end capping to obtain a tertiary alcohol end capping product;
2) the tertiary alcohol end capping product is subjected to intramolecular dehydration under the action of a Lewis acid catalyst to obtain a double-bond end capping product;
the active hydrogen-containing group is one or more of primary amino, secondary amino, primary hydroxyl and secondary hydroxyl;
the molar ratio of epoxy isobutane to the active hydrogen in the substrate is 1: 1-1.5: 1;
the substrate is one or more of ethylenediamine, trimethylolpropane, ethanolamine, pentaerythritol, sorbitol, methanol and ethylamine.
2. The method of synthesis according to claim 1, further comprising, before performing the reaction in step 1), the steps of: removing water from the substrate for reaction with the epoxyisobutane.
3. The method of claim 2, wherein when the active hydrogen-containing group comprises at least one of a primary or secondary hydroxyl group, prior to the step of removing water from the substrate, further comprising the step of: contacting the substrate with a basic catalyst.
4. The synthesis method according to claim 3, wherein the substrate and the basic catalyst are contacted under a nitrogen atmosphere, the contact is carried out at a temperature of 80-120 ℃, and the contact is carried out under a pressure condition of-0.09 to-0.1 MPa; the contact time is 1-3 h.
5. The synthesis process according to claim 3, characterized in that the basic catalyst is used in an amount of 0.1-1% by mass of the substrate.
6. The synthesis method according to claim 3, wherein the basic catalyst is selected from one or more of alkali metal hydroxide and alkali metal alkoxide.
7. The synthesis method according to claim 6, wherein the basic catalyst is selected from one or more of sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide.
8. The method of synthesis according to claim 6, further comprising, after step 2), the steps of: adding a neutralizing agent to the prepared double bond end-capped product to neutralize the basic catalyst.
9. The synthesis method as claimed in claim 1, wherein the reaction temperature in step 1) is 100-150 ℃; the reaction pressure is 0.05-0.5 MPa; the reaction time is 1-10 h.
10. The method of claim 1, wherein in step 2), the lewis acid catalyst is a solid heterogeneous lewis acid catalyst.
11. The synthesis method of claim 10, wherein the lewis acid catalyst is selected from one or more of aluminum halide, iron halide, zinc halide, boron halide, aluminum oxide, iron oxide, and zinc oxide; the specific surface area of the solid heterogeneous phase Lewis acid catalyst is less than or equal to 2000m2/g。
12. The synthesis method according to claim 11, wherein the specific surface area of the solid heterogeneous Lewis acid catalyst is 300-1500 m2/g。
13. The synthesis method according to claim 1, wherein the reaction of step 2) is carried out in a fixed bed, and the reaction temperature is 80-150 ℃; the feeding mass airspeed is 0.5-10 h-1。
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| EP0389302A1 (en) * | 1989-03-23 | 1990-09-26 | Riker Laboratories, Inc. | Olefinic 1H-imidazo [4,5-c]quinolin-4-amines |
| CN107245083A (en) * | 2017-06-08 | 2017-10-13 | 中国科学技术大学 | 2,8,9 trioxa, 5 azepine, 1 germanium two ring [3.3.3] hendecane class compound and preparation method thereof |
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| EP0389302A1 (en) * | 1989-03-23 | 1990-09-26 | Riker Laboratories, Inc. | Olefinic 1H-imidazo [4,5-c]quinolin-4-amines |
| CN107245083A (en) * | 2017-06-08 | 2017-10-13 | 中国科学技术大学 | 2,8,9 trioxa, 5 azepine, 1 germanium two ring [3.3.3] hendecane class compound and preparation method thereof |
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