[go: up one dir, main page]

WO2016113761A1 - Catalyseur à base d'acide de lewis sur support polymère hydrophobe et procédé de préparation associé - Google Patents

Catalyseur à base d'acide de lewis sur support polymère hydrophobe et procédé de préparation associé Download PDF

Info

Publication number
WO2016113761A1
WO2016113761A1 PCT/IN2016/050016 IN2016050016W WO2016113761A1 WO 2016113761 A1 WO2016113761 A1 WO 2016113761A1 IN 2016050016 W IN2016050016 W IN 2016050016W WO 2016113761 A1 WO2016113761 A1 WO 2016113761A1
Authority
WO
WIPO (PCT)
Prior art keywords
poly
lewis acid
polymer
catalyst
dvb
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IN2016/050016
Other languages
English (en)
Inventor
Nayaku Nivrati Chavan
Surendra PONRATHNAM
Sachin Tanaji MANE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Publication of WO2016113761A1 publication Critical patent/WO2016113761A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/027—Polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups

Definitions

  • the present invention relates to a hydrophobic poly (Allylamine-co-divinylbenzene) [poly(AA-co-DVB)] supported Lewis acid catalyst for anhydrous reaction which exhibits high loading and avoids the leakage problem of catalyst during application.
  • present invention relates to the immobilization of Lewis acid catalyst on poly(AA-co-DVB) which can be easily recovered, recycled, and repeatedly used in various organic transformations or chemical reactions. More particularly, present invention relates to polymer-supported Lewis acid catalyst useful in synthesis of polyimine.
  • US 2009/0110907 Al relates to polymer membranes that include a crosslinked poly(vinyl alcohol-co-vinylamine), which are non-porous or are porous with pores having a median pore size of 300 nm or less.
  • US 5,770,539 relates to Lewis acid catalysts which are immobilized on a porous polymer substrate.
  • E.P. Pat. No. 1,997,555 Bl relates to immobilized Lewis acids which act as a catalyst and can be used in various chemical reactions for more turn over number without any loss of activity.
  • E.P. Pat. No. 1, 184,076 Bl relates to a novel Lewis acid catalyst which shows high reactivity even in an aqueous medium without the use of organic solvents, is easily prepared, recovered, and is excellent in reusability, and to methods of organic synthesis using such a novel Lewis acid catalyst.
  • WO 2004003044 A2 relates to polymers capable of sustaining and/or promoting a process involving the exchange of the regular repeating monomer units presented in the form of a polyhydrazone or a polyimine, polymerized by repeating alternating units of dihydrazides and/or diamines and dialdehydes, but not limited to these two polymers and may also include other alternating co-polymers, defined as Dynamers.
  • Al cross-linked poly(allylamine) is prepared by crosslinking of poly(allylamine) with epichlorohydrin (PAAEPI), branched poly(allylamine) prepared by branching of poly(allylamine) with divinylbenzene (PAADVB) with mol. wt. in the range of 500 to 2200 g/mol.
  • PAAEPI epichlorohydrin
  • PAADVB divinylbenzene
  • US 3,506,613 relates to reacting an aliphatic or aromatic substituted aliphatic diketone and an aliphatic diamine such that they results a linear, non cross-conjugated polymer.
  • US 3,668, 183 relates to polyenamine resins useful as adhesives and in coating applications are produced from the reaction of polyacetoacetates or polyacetoacetamides with blocked polyamines.
  • the blocked polyamines are ketimines or enamines obtained by the reaction of an amine or amide with either a ketone or an aldimine obtained by the reaction of an amine or amide with an aldehyde.
  • US 2,352,387 relates to the process of producing condensation products which consists of condensing a primary aliphatic diamine containing at least 6 carbon atoms and only two amino groups with a monomeric carbonyl compound selected from the class consisting of aldehydes and ketones in the molecular ratio of about one carbonyl group of the carbonyl compounds for each amino group of the diamine.
  • US 3,461, 100 relates to a polymeric material for use as a protective coating, which is insoluble in water but soluble in a common aliphatic hydrocarbon solvent, can be produced by condensing an aldehyde or ketone (formaldehyde) with a diamine (hexamethylenediamine) in organic medium while continuously removing by-product water.
  • an aldehyde or ketone formaldehyde
  • diamine hexamethylenediamine
  • Lewis acids which were potentially used in organic synthesis are aluminium chloride, stannous chloride, mercury chloride, boron trifluoride, and titanium tetrachloride.
  • Different methods including immobilization, encapsulation, coordinate complex, anchoring (covalent), and entrapment are widely used to support the Lewis acids onto the porous polymer matrix.
  • Leakage and small loading of catalysts are the major concern with applications of supported species.
  • polymer-supported Lewis acid was used in high temperature reactions, consequently, thermal stability of base polymer and polymer-supported Lewis acid was studied before the use in solid-phase synthesis.
  • the main objective of the present invention is to provide a thermostable hydrophobic poly(AA-co-DVB) supported Lewis acid catalyst which exhibits high loading and avoids the leakage problem of catalyst during application in reaction.
  • Another objective of the present invention is to provide a process for the synthesis of hydrophobic poly(AA-co-DVB) supported Lewis acid as a catalyst for anhydrous reaction.
  • Yet another objective of the present invention is to provide a polymer-supported Lewis acid catalyst for the synthesis of polyimine.
  • present invention provides a hydrophobic poly(Allylamine-co- divinylbenzene) [poly(AA-co-DVB)] supported Lewis acid catalyst comprising poly(Allylamine-co-divinylbenzene) [poly(AA-co-DVB)] in the range of 60 to 90 wt% and Lewis acid in the range of 10 to 40wt%.
  • present invention provides a process for the synthesis of hydrophobic poly(AA-co-DVB) supported Lewis acid catalyst comprising the steps of:
  • step (b) polymerizing the reaction mixture as obtained in step (a) by heating the reactor and obtain the product in the form of beads which on purification affords the copolymer [poly(AA-co-DVB)] in 70-80% yields; c. adding Lewis acid solution to copolymer as obtained in step (b) followed by washing and drying to affords poly(AA-co-DVB) supported Lewis acid catalyst.
  • Lewis acids used is selected from aluminium chloride or stannous chloride.
  • said catalyst is thermostable upto 400°C and useful for high temperature reactions.
  • said catalyst exhibit glass transition temperature upto 240°C.
  • said catalyst is recyclable and reusable.
  • said catalyst is useful to avoids the catalyst leakage during organic transformations.
  • present invention provides a process for the synthesis of polyimine using the catalyst as claimed in claim 1, and the said process comprising the steps of:
  • step (a) a. mixing 4,4'-diacetylbiphenyl, N-methyl-2-pyrrolidone and poly(AA-co- DVB) supported Lewis acid catalyst followed by stirring and adding para phenylene diamine and stirring to obtain the reaction mixture; b. filtering the reaction mixture as obtained in step (a) to recover poly(AA- co-OV ) supported Lewis acid catalyst and adding alcohol to the filtrate to form precipitate which on filtration, washing, and drying furnishes the desired product polyimine.
  • alcohol used is preferably ethanol
  • Figure 1 depicts Fourier transform infrared (FT-IR) spectrum of base (ADC) and polymer-supported Lewis acid(ADCA and ADCS).
  • Figure 2 depicts average particle size of base and polymer-supported Lewis acid.
  • Figure 3 depicts DTG thermograms of base and polymer-supported Lewis acid.
  • Figure 4 depicts DSC thermograms of base and polymer-supported Lewis acid.
  • Figure 5 depicts swelling ratio of polymer-supported Lewis acid.
  • Figure 6 depicts Scanning electron microscopy (SEM) images of base (ADC) and polymer-supported Lewis acid (ADCA and ADCS) for 5% and 25% crosslink density
  • Figure 7 depicts EDX analysis of polymer-supported Lewis acid (a) wt%, and (b) at%
  • Figure 8 depicts 1H MR of polyimine.
  • Figure 9 depicts DTG thermograms of polyimine.
  • Scheme 1 represents process steps for the synthesis of poly(AA-co-DVB) and its modification with Lewis acid.
  • Scheme 2 represents process steps for the synthesis of polyimine.
  • thermostable hydrophobic poly(AA-co-DVB) supported Lewis acid catalyst which exhibits high loading and avoids the leakage problem of catalyst during application in reaction.
  • the present invention provides a process for the synthesis of hydrophobic poly(AA- co-DVB) supported Lewis acid catalyst which is used in an organic synthesis and functional group transformation reactions.
  • Hydrophobic poly(AA-co-DVB) supported Lewis acid catalyst was used for anhydrous reaction, wherein the Lewis acid is bonded to the polymer support through a coordinate bond.
  • the present invention provides a process for the synthesis of poly(AA-co-DVB) using cyclohexanol as a porogen at different crosslink densities and its modification with Lewis acid comprising:
  • step (b) adding Lewis acid solution (in ethanol) to polymer of step (b), to obtain the modified polymer which on washing and drying affords the polymer modified Lewis acid.
  • the above process for the synthesis of poly(AA-co-DVB) and its modification with Lewis acid is shown in Scheme 1.
  • the present invention provides a process wherein Lewis acids used is preferably selected from aluminum chloride (A1C1 3 ) or stannous chloride (SnCl 2 ).
  • the present invention provides a process for the synthesis of polyimine using poly(AA-co-DVB) supported AlCl 3 /SnCl 2 catalyst comprising the steps of:
  • step (b) On completion of reaction time, filtering the reaction mixture of step (a) to recover polymer-supported AICI3 or SnCl 2 and adding methanol to the filtrate to form precipitate which on filtration, washing, and drying furnishes the desired product.
  • the present invention provides polymer-supported catalyst which is thermostable and useful for high temperature reactions.
  • the present invention provides polymer-supported catalyst with thermostability up to 400°C and glass transition temperature up to 240°C.
  • the present invention provides polymer-supported catalyst which is useful to recover, recycle, and reuse of the catalyst which make the process environmentally benign and industrially economical.
  • the swelling behavior of the polymer-supported catalyst was also examined for different solvents to decide the compatibility of polymer with solvent.
  • the present invention provides a polymer with more loading of Lewis acid catalyst as well as to avoid the catalyst leakage during application.
  • the polymers obtained by suspension polymerization were purified by soxhlet extraction method to remove unreacted and adsorbed reaction composition.
  • Fourier transform infrared (FT-IR) spectra were recorded on Perkin Elmer spectrophotometer having model spectrum GX.
  • the samples for FTIR were prepared after drying the polymers at 80°C for 8 h.
  • Surface area of polymer was determined by nitrogen adsorption/desorption isotherm (BET method) using surface area analyzer NOVA 2000e, Quantachrome.
  • average particle diameter was determined using an Accusizer 780 (model LE 2500-20) PSS.NICOMP Particle sizing system, Santa Barbara, California, USA.
  • Amine content of unmodified polymer was determined by acetic anhydride in pyridine, titrimetrically.
  • Thermal stability (TGA) of polymers was studied by simultaneous thermal analysis (STA, Perkin Elmer) while glass transition temperature was evaluated using differential scanning calorimetry Q10 (Thermal analysis). Swelling ratio of polymers was determined by wt/wt ratio. Scanning electron microscopy (SEM) was used for external morphology and particle visualization which were performed by Quanta 200-3D, dual beam ESEM microscope wherein electron source was thermionic emission tungsten filament.
  • Suspension polymerization was carried out in a double walled cylindrical glass reactor maintained at a constant temperature, equipped with a condenser, nitrogen inlet, and overhead stirrer.
  • the oil phase comprising 11.147 g (0.195 mol) of allylamine, 1.271 g (0.01 mol) of divinylbenzene, 2.5 mol% of 2,2'- azobisisobutyronitrile, and 48 mL of cyclohexanol (porogen) were added to the suspension reactor containing 1 wt% of poly(vinylpyrrolidone) as a protective colloid dissolved in 200 mL of distilled water with constant stirring speed of 500 rotations per min.
  • Table 1 Feed composition of allylamine and divinylbenzene at different crosslink density
  • Reaction conditions Batch size: 16 mL, 2,2'-azobisisobutyronitrile (AIBN): 2.5 mol%, stirring speed: 500 rpm, reaction time: 3 h, outer phase: H 2 0, protective colloid: poly(vinylpyrrolidone), concentration of protective colloid: 1 wt%, porogen: cyclohexanol; porogen concentration - 48 mL (monomenporogen ratio, 1 :3 v/v).
  • AIBN 2,2'-azobisisobutyronitrile
  • Polymers obtained by suspension polymerization were purified by soxhlet extraction method to remove low molecular weight polymer and unreacted ingredients.
  • Methanol was used as an extracting solvent since unreacted monomer, adsorbed PVP, and porogen are soluble/miscible in methanol.
  • One Liter of distilled methanol was added in round bottom flask of soxhlet apparatus. Subsequently, polymer beads were packed in whatmann paper, placed in soxhlet apparatus, and methanol was refluxed. After 5 methanol cycles, polymer was filtered and again washed with methanol. Later on, polymer beads were dried at 60°C under reduced pressure.
  • the amine content determination is the polymer reactivity measurement and was evaluated by using acetic anhydride in pyridine, titrimetrically. It was observed that, amine content was decreased with increase in crosslink density. This is mainly due to concentration of allylamine was decreased with increase in crosslink density of polymer. Observed amine content was lower than theoretical due to large number of amine functionality are buried into the polymer matrix and are not available for titrimetric determination. Amine content (theoretical and observed) of crosslinked base polymer is reported in Table 2. Table 2: Amine content (theoretical and observed) of unmodified base polymer
  • DSC Differential scanning calorimetry
  • Swelling ratio provides a suitable solvent for solid phase synthesis.
  • Base polymer and polymer-supported Lewis acid demonstrated the higher swelling for low crosslink density polymer.
  • low crosslink density polymer-supported Lewis acid is useful as a catalyst in organic reactions. This is mainly due to the low crosslink density polymer reveals higher swelling as well as more reactivity tends to more catalyst loading.
  • Solubility parameter was used to calculate polymer-solvent interaction parameter. Generally, each solvent can swell the polymer to a certain extent. This extent of swelling depends on the solubility parameter of polymer and swelling solvent, polymer-solvent interaction parameter, and degree of crosslinking of polymer. Solubility parameter of polymer (calculated) and swelling solvents (referred) are reported in Table 3.
  • Ds degree of swelling
  • Ws weight of swollen polymer at a given time
  • W d weight of a dried polymer.
  • Swelling measurements were carried out by storing 0.5 g of polymer matrix in 20 mL of ethanol/acetonitrile/l,4-dioxane at room temperature for 24 h to attain equilibrium swelling. Swelling ratio of crosslinked polymer was determined by measuring the weight of the polymer after equilibrium swelling in a solvent (W s ) and after drying (W d ) of polymer.
  • Swelling ratio was measured as a function of polymer-solvent interaction parameter and crosslink density. Solubility parameter difference of poly(AA-co-DVB) and 1,4- dioxane is smaller and difference was increased for acetonitrile and further for ethanol. Swelling behaviour of a polymer is in accordance to solubility parameter difference between polymer and swelling solvent. It was observed that, smaller the polymer-solvent interaction parameter more is the swelling of polymer and vice-versa. Results demonstrate that, swelling ratio is dependent on the crosslink density. Swelling ratio was lower for higher crosslink density polymer.
  • SEM images of base polymer and polymer-supported Lewis acids were scanned for 5% and 25% crosslink density with 2500X magnification. For this, polymer beads were mounted on grid and placed below electron beam to observe the surface morphology of polymers. It is worth noting that, external morphology revealed the porous nature of polymer beads before and after modification with Lewis acid. SEM images of base polymer and polymer-supported Lewis acid is represented in Fig. 6.
  • EDX analysis of base polymer and polymer-supported Lewis acid was evaluated by Quanta 200-3D, dual beam ESEM microscope with thermionic emission tungsten filament as an electron source. It was observed that, base polymer contains carbon and nitrogen only. However, polymer-supported Lewis acid demonstrated the presence of aluminium, tin, and chlorine in their respective copolymers. It was also observed that, percentage of aluminium and tin was lower with high crosslink density polymer. Results revealed that, the presence of aluminium (10 wt%/5.18 at%) and tin (33.02 wt% / 5.30 at%) at 5% cross-link density. Hydrogen in the polymer was not detected due to instrument limitation. EDX analysis of base and polymer-supported Lewis acid in wt% and at% is represented in Fig. 7. EXAMPLE 2
  • Suspension polymerization was carried out in a double walled cylindrical glass reactor maintained at a constant temperature, equipped with a condenser, nitrogen inlet and overhead stirrer.
  • the oil phase comprising 10.256 g (0.180 mol) of allylamine, 2.339 g (0.018 mol) of divinylbenzene, 2.5 mol% of 2,2'-azobisisobutyronitrile, and 48 mL of cyclohexanol (porogen) were added to the suspension reactor containing 1 wt% of poly(vinylpyrrolidone) as a protective colloid dissolved in 200 mL of distilled water with constant stirring at 500 rotations per min.
  • the temperature of the reactor was raised to 70°C and maintained for 3 h to carry out the polymerization.
  • the product obtained in the form of beads was cooled, filtered, and washed several times with water, methanol, and dried in oven at 60°C under reduced pressure for 8 h.
  • Suspension polymerization was carried out in a double walled cylindrical glass reactor maintained at a constant temperature, equipped with a condenser, nitrogen inlet and overhead stirrer.
  • the oil phase comprising 9.496 g (0.166 mol) of allylamine, 3.248 g (0.025 mol) of divinylbenzene, 2.5 mol% of 2,2' azobisisobutyronitrile, and 48 mL of cyclohexanol (porogen) were added to the suspension reactor containing 1 wt% of poly(vinylpyrrolidone) as a protective colloid dissolved in 200 mL of distilled water with constant stirring at 500 rotations per min.
  • Suspension polymerization was carried out in a double walled cylindrical glass reactor maintained at a constant temperature, equipped with a condenser, nitrogen inlet and overhead stirrer.
  • the oil phase comprising 8.842 g (0.155 mol) of allylamine, 4.033 g (0.031 mol) of divinylbenzene, 2.5 mol% of 2,2' azobisisobutyronitrile, and 48 mL of cyclohexanol (porogen) were added to the suspension reactor containing 1 wt% of poly(vinylpyrrolidone) as a protective colloid dissolved in 200 mL of distilled water with constant stirring at 500 rotations per min.
  • the temperature of the reactor was raised to 70°C and maintained for 3 h to carry out the polymerization.
  • the product obtained in the form of beads was cooled, filtered, and washed several times with water, methanol, and dried in oven at 60°C under reduced pressure for 8 h.
  • Suspension polymerization was carried out in a double walled cylindrical glass reactor maintained at a constant temperature, equipped with a condenser, nitrogen inlet and overhead stirrer.
  • the oil phase comprising 8.271 g (0.145 mol) of allylamine, 4.716 g (0.036 mol) of divinylbenzene, 2.5 mol% of 2,2' azobisisobutyronitrile, and 48 mL of cyclohexanol (porogen) were added to the suspension reactor containing 1 wt% of poly(vinylpyrrolidone) as a protective colloid dissolved in 200 mL of distilled water with constant stirring at 500 rotations per min.
  • the temperature of the reactor was raised to 70°C and maintained for 3 h to carry out the polymerization.
  • the product obtained in the form of beads was cooled, filtered, and washed several times with water, methanol, and dried in oven at 60°C under reduced pressure for 8 h.
  • the yield of the copolymer was 70-80% for different crosslink density.
  • Soxhlet purified polymer was used for modification with Lewis acid (A1C1 3 ).
  • Poly(AA-co-DVB) having crosslink densities of 5, 10, 15, 20, and 25% were used for modification with AICI3.
  • Lewis acid (AICI3 , 5 g) was dissolved in 50 mL of ethanol and placed at room temperature for 2 days for complete dissolution of Lewis acid.
  • ADC (5% to 25% crosslink) polymer (2 g) was weighed in a glass vial. To this, above Lewis acid solution (10 mL of A1C1 3 solution in ethanol) was added to each crosslink density polymer. Then, these modified polymers were placed for 2 days to obtain the uniform polymer modification. Subsequently, polymers were washed with ethanol for 3 - 4 times to remove unreacted Lewis acid and dried at 70°C under reduced pressure. Dried polymers were used for characterization.
  • Soxhlet purified polymer was used for modification with Lewis acids (SnCl 2 ).
  • Poly(AA-co-DVB) having crosslink densities of 5, 10, 15, 20, and 25% were used for modification with SnCl 2 .
  • Lewis acid (SnCl 2; 5 g) was dissolved in 50 mL of ethanol and placed at room temperature for 2 days for complete dissolution of Lewis acid.
  • ADC (5% to 25% crosslink) polymer (2 g) was taken separately in a glass vial, to this above Lewis acid solution (10 mL of SnCl 2 solution in ethanol) was added to each crosslink density polymer. Then, these modified polymers were placed for 2 days to obtain the uniform polymer modification. Subsequently, polymers were washed with ethanol for 3 - 4 times to remove unreacted Lewis acid and dried at 70°C under reduced pressure. Dried Polymers were used for characterization.
  • the hydrophobic polymer-supported Lewis acid can be used in anhydrous reaction.
  • the hydrophobic polymer-supported Lewis acid has wide applications in different organic transformations for number of cycles because of recovery, recycle, and reusable properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un acide de Lewis sur support poly(AA-co-DVB) hydrophobe comme catalyseur hétérogène pour réaction anhydre. Ces catalyseurs à base d'acide Lewis sur support polymère non modifié et sur polymère ont été caractérisés par différentes techniques telles que la surface, la dégradation thermique, la température de transition vitreuse, la réactivité, et le comportement de gonflement. Un polymère hydrophobe et plus réactif a été sélectionné pour être utilisé comme catalyseur dans une réaction anhydre. Globalement, l'invention concerne un procédé pour la synthèse d'un catalyseur à base d'acide de Lewis sur support poly (AA-co-DVB) hydrophobe et son utilisation pour une réaction anhydre.
PCT/IN2016/050016 2015-01-15 2016-01-15 Catalyseur à base d'acide de lewis sur support polymère hydrophobe et procédé de préparation associé Ceased WO2016113761A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN128DE2015 2015-01-15
IN128/DEL/2015 2015-01-15

Publications (1)

Publication Number Publication Date
WO2016113761A1 true WO2016113761A1 (fr) 2016-07-21

Family

ID=55661502

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2016/050016 Ceased WO2016113761A1 (fr) 2015-01-15 2016-01-15 Catalyseur à base d'acide de lewis sur support polymère hydrophobe et procédé de préparation associé

Country Status (1)

Country Link
WO (1) WO2016113761A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113398991A (zh) * 2021-05-26 2021-09-17 华东理工大学 疏水型锆负载强酸性阳离子交换树脂催化剂的制备方法及应用

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2352387A (en) 1939-06-07 1944-06-27 Gen Aniline & Film Corp Process for the production of condensation products
US3461100A (en) 1964-07-02 1969-08-12 Tracor Condensation products of aldehydes or ketones with diamines and monoamines
US3506613A (en) 1969-01-15 1970-04-14 Owens Illinois Inc Novel polymers prepared from aliphatic diketones and aliphatic diamines
US3668183A (en) 1970-11-03 1972-06-06 Union Carbide Corp Production of polyenamines
GB1298678A (en) * 1969-10-31 1972-12-06 Bba Group Ltd Polyimines
US4000187A (en) 1972-04-11 1976-12-28 University Of Iowa Research Foundation Quinoline and anthrazoline polymers
WO1994028037A1 (fr) * 1993-05-20 1994-12-08 Exxon Chemical Patents Inc. Catalyseurs a l'acide de lewis maintenu en support sur un substrat polymere poreux
WO2004003044A2 (fr) 2002-06-28 2004-01-08 Jean-Marie Lehn Dynameres: materiaux polymeriques a formation reversible et a echange de composants
EP1069127B1 (fr) 1998-02-13 2007-08-08 Japan Science and Technology Agency Acide de lewis micro-encapsule
US20090110907A1 (en) 2007-10-29 2009-04-30 Jiang Dayue D Membranes Based On Poly (Vinyl Alcohol-Co-Vinylamine)
EP1184076B1 (fr) 1999-11-17 2010-04-21 Japan Science and Technology Agency Catalyseur a base d'acide de lewis sur support polymere
US20110139466A1 (en) 2009-12-10 2011-06-16 Schlumberger Technology Corporation Ultra high temperature packer by high-temperature elastomeric polymers
EP1997555B1 (fr) 2006-03-10 2013-02-27 Japan Science and Technology Agency Catalyseurs acide de lewis immobilises enduits de liquides ioniques et leur utilisation
US20140241966A1 (en) 2012-10-25 2014-08-28 Georgia Tech Research Corporation Supported poly(allyl)amine and derivatives for co2 capture from flue gas or ultra-dilute gas streams such as ambient air or admixtures thereof

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2352387A (en) 1939-06-07 1944-06-27 Gen Aniline & Film Corp Process for the production of condensation products
US3461100A (en) 1964-07-02 1969-08-12 Tracor Condensation products of aldehydes or ketones with diamines and monoamines
US3506613A (en) 1969-01-15 1970-04-14 Owens Illinois Inc Novel polymers prepared from aliphatic diketones and aliphatic diamines
GB1298678A (en) * 1969-10-31 1972-12-06 Bba Group Ltd Polyimines
US3668183A (en) 1970-11-03 1972-06-06 Union Carbide Corp Production of polyenamines
US4000187A (en) 1972-04-11 1976-12-28 University Of Iowa Research Foundation Quinoline and anthrazoline polymers
WO1994028037A1 (fr) * 1993-05-20 1994-12-08 Exxon Chemical Patents Inc. Catalyseurs a l'acide de lewis maintenu en support sur un substrat polymere poreux
US5770539A (en) 1993-05-20 1998-06-23 Exxon Chemical Patents Inc. Lewis acid catalysts supported on porous polymer substrate
EP1069127B1 (fr) 1998-02-13 2007-08-08 Japan Science and Technology Agency Acide de lewis micro-encapsule
EP1184076B1 (fr) 1999-11-17 2010-04-21 Japan Science and Technology Agency Catalyseur a base d'acide de lewis sur support polymere
WO2004003044A2 (fr) 2002-06-28 2004-01-08 Jean-Marie Lehn Dynameres: materiaux polymeriques a formation reversible et a echange de composants
EP1997555B1 (fr) 2006-03-10 2013-02-27 Japan Science and Technology Agency Catalyseurs acide de lewis immobilises enduits de liquides ioniques et leur utilisation
US20090110907A1 (en) 2007-10-29 2009-04-30 Jiang Dayue D Membranes Based On Poly (Vinyl Alcohol-Co-Vinylamine)
US20110139466A1 (en) 2009-12-10 2011-06-16 Schlumberger Technology Corporation Ultra high temperature packer by high-temperature elastomeric polymers
US20140241966A1 (en) 2012-10-25 2014-08-28 Georgia Tech Research Corporation Supported poly(allyl)amine and derivatives for co2 capture from flue gas or ultra-dilute gas streams such as ambient air or admixtures thereof

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
A. P. DESHMUKH ET AL.: "Friedel Crafts acylation reaction using polymer-supported aluminium chloride", J CHEM. RES., 1999, pages 568 - 569
D. C. NECKERS ET AL.: "Polymer-protected reagents. Polystyrene-aluminum chloride", 1NT.J AM. CHEN . SOC., vol. 94, no. 26, 1972, pages 9284 - 9285
I. KULSZEWICZ-BAJER ET AL.: "Heteropolyanions doped polyimine-preparation and spectroscopic properties", MATER. RES. BULL., vol. 30, 1995, pages 1571 - 1578
J. LU ET AL.: "Organic polymer supports for synthesis and for reagent and catalyst immobilization", CHEM. REV., vol. 109, no. 2, 2009, pages 815 - 838
K. SUEMATSU ET AL.: "Polyimine, a C=N double bond containing polymers: synthesis and properties", POLYM. J, vol. 15, 1983, pages 71 - 79
M. E. LANDIS ET AL.: "Cycloreversion of quadricyclane to norbornadiene catalyzed by Tin (II) complexes", TETRAHEDRON LETT., vol. 23, no. 4, 1982, pages 375 - 378
M. H. MOHAMED ET AL.: "Porous copolymer resins: tuning pore structure and surface area with non reactive porogens", NANOMATERIALS, vol. 2, 2012, pages 163 - 186
R. KITA ET AL.: "Hydrophilic polymer supports for solid-phase synthesis: preparation of poly(ethylene glycol) methacrylate polymer beads using ''classical'' suspension polymerization in aqueous medium and their application in the solid-phase synthesis of hydantoins", J COMB. CHEM., vol. 3, 2001, pages 564 - 571
RAN RUICHENG ET AL.: "Polymer-supported Lewis acid catalysts. VI. Polystyrene-bonded stannic chloride catalyst", CHINESE J. POLYM. SCI., vol. 9, no. 1, 1991, pages 79 - 85

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113398991A (zh) * 2021-05-26 2021-09-17 华东理工大学 疏水型锆负载强酸性阳离子交换树脂催化剂的制备方法及应用

Similar Documents

Publication Publication Date Title
US11535703B2 (en) Methanesulfonic acid mediated solvent free synthesis of conjugated porous polymer networks
CN1028534C (zh) 一氧化碳与不饱和化合物的聚合物的制备方法
EP2832767A1 (fr) Procédé pour la synthèse de structures organiques covalentes
US8110519B2 (en) Polymer-supported metal cluster composition
JP4295096B2 (ja) ２個以上のヘテロ原子を含有する架橋された二環式および多環式のオレフィンの開環メタセシス重合
WO2008150033A1 (fr) Copolymère alterné stéréosélectif époxy-dioxyde de carbone
CN104817691B (zh) 聚烯醚类化合物及其制备方法
Boztepe et al. Heterogenization of homogeneous NHC-Pd-pyridine catalysts and investigation of their catalytic activities in Suzuki-Miyaura coupling reactions
CN109746045A (zh) 一种有机多孔聚合物负载钯催化剂及其制备方法和应用
CN110818867A (zh) 一种超交联聚合物及其制备方法和应用
CN113683767B (zh) 一种聚烯醚类化合物及其制备方法与应用
Li et al. Temperature-responsive hairy particle-supported proline for direct asymmetric aldol reaction in water
WO2016113761A1 (fr) Catalyseur à base d'acide de lewis sur support polymère hydrophobe et procédé de préparation associé
CN1036785C (zh) 催化剂组合物及其在制备聚合物方法中的应用
Yangirov et al. Diphenyl oxide copolyarylenephthalides with different ratio of phthalide and diphthalide groups
Havelková et al. Functionalized hyper-cross-linked porous homopolymers of ring-substituted 1, 3-diethynylbenzenes and their physisorption activity
CN110327973A (zh) 一种交联降冰片烯共聚物/炭黑三维网络负载铜纳米催化剂及其制备方法与应用
CN110339860B (zh) 交联降冰片烯共聚物复合炭黑三维网络固载铂纳米催化剂及其制备方法和应用
Debnath et al. Synthesis of polymer microsphere‐supported chiral pyrrolidine catalysts by precipitation polymerization and their application to asymmetric Michael addition reactions
Wang et al. Cyclodextrin-based hyperbranched polymers by acyclic diene metathesis polymerization of an ABn monomer: molecule design, synthesis, and characterization
CN108097306B (zh) 一种双功能化的氧化硅催化材料及其制备和应用
Kabir et al. Enhancing CO2 Transport Across the PEG/PPG‐Based Crosslinked Rubbery Polymer Membranes with a Sterically Bulky Carbazole‐Based ROMP Comonomer
Kim et al. Construction of late transition metal complex on amine-functionalized SiO2 and SBA-15 for L-lactide polymerization
Penchev et al. Synthesis of polyphenylacetylene by iron (III) chloride catalyzed carbonyl olefin metathesis polymerization of chalcone
CN106543424A (zh) 一种聚碳酸亚丙酯/poss杂化材料及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16714553

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16714553

Country of ref document: EP

Kind code of ref document: A1