CN102500416A - Synthesis and preparation methods of polymer particle type esterification catalyst containing sulfonic acid groups - Google Patents
Synthesis and preparation methods of polymer particle type esterification catalyst containing sulfonic acid groups Download PDFInfo
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- CN102500416A CN102500416A CN2011103090843A CN201110309084A CN102500416A CN 102500416 A CN102500416 A CN 102500416A CN 2011103090843 A CN2011103090843 A CN 2011103090843A CN 201110309084 A CN201110309084 A CN 201110309084A CN 102500416 A CN102500416 A CN 102500416A
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Abstract
The invention relates to a polymer particle type esterification catalyst containing sulfonic acid groups and a preparation method thereof, belonging to the field of the ion exchange resin type catalyst. The catalyst is in a porous structure, has a large specific surface area, is easy to separate and convenient for post-processing and can be directly used for the catalytic esterification reaction. The resin type catalyst is prepared by synthesizing by using an inverse emulsion polymerization method. The synthesizing monomers are mainly water-soluble sulfonic acid groups containing olefins, and the crosslinking agents are mainly water-soluble bi-functionality or tri-functionality monomers containing double bonds. The crosslinked network-like resin microspheres are obtained through inverse emulsion polymerization, and the sulfonic acid groups are introduced in through the sulfonic acid monomers, thus the resin type catalyst has the characteristic of catalysis for esterification reaction. The resin type catalyst which has a high porosity, a large specific surface area and good catalytic performance, is easy to separate and is recyclable is synthesized through controlling the type, the content and the ratio of the emulsifier, the content of the crosslinking agents and the type of the pore-forming agent. The raw materials for synthesizing the resin type catalyst have a wide source, low cost and great industrial value.
Description
Technical field
The present invention relates to a kind of preparation that contains sulfonic polymeric particles type catalyst for esterification reaction, this catalyst belongs to the ion exchange resin type catalyst that contains loose structure.
Background technology
Acrylic acid ester is important high polymer monomer and basic Organic Chemicals, and considerable status is arranged in the application of fine chemistry industry, and its series of products are thousands of, almost relate to industrial circle all departments.Ester is acid and the pure one type of organic compound that reacts and generate.This reaction is reversible reaction, in order to improve reaction speed, improves the conversion ratio of esterification, in the process of synthetic ester, usually adds acidic catalyst, can improve its reaction speed and output greatly.
Traditional catalyst has strong inorganic acid catalyst, but accessory substance is many in the synthetic product, and problems such as separation difficulty, contaminated environment are arranged.Solid catalyst has easily separated, capable of circulation as one type of novel catalyst for esterification reaction, characteristics such as high catalytic efficiency are widely used; Wherein representative solid catalyst is the ion exchange resin type porous catalyst, is characterized in having good pore structure, has bigger surface area; Good stability, strong acid character, high catalytic performance; And hear resistance is good, and catalytic process is stable.But conventional ion exchanger resin type catalyst need carry out complicated sulfonation process before carrying out catalysis.And the present invention does not need sulfonation through the synthetic resin type catalyst of antiphase emulsifiable method, because of its resin itself has sulfonic acid group, can directly carry out catalytic esterification.Thereby reached synthetic convenience, used purposes such as quick, be more suitable for suitability for industrialized production.Therefore syntheticly contain sulfonic resin catalyst crucial meaning is arranged.
Say in theory, can be through selecting emulsifier type, the content of emulsifying agent; The proportioning of compound emulsifying agent, content of crosslinking agent, the kind of pore-foaming agent; It is moderate that the control extent of reaction obtains particle diameter; The aperture homogeneous, the resin microsphere that form is better and catalytic performance is high, and catalytic esterification repeatedly.
Summary of the invention
One of the object of the invention is to adopt the synthetic a kind of nonexpondable sulfonic group polymeric particles type catalyst for esterification reaction that contains capable of circulation of inverse emulsion polymerization method; It is characterized in that this catalyst contains sulfonic group; Capable of circulationly repeatedly use and keep advantages of high catalytic activity; Catalytic process is stable, and this catalyst is used for esterifications such as catalysis acrylic ester synthesizing, and its structural formula is shown in (I):
N wherein, m is the integer greater than 1, can be identical or different;
R
1Be hydrogen atom or methyl;
R
2, R
3, R
4, R
5Be selected from and contain different phenyl ring or amide groups or different carbon chain lengths alkyl group, R
2, R
3, R
4, R
5Identical or different.Include but not limited to 2-acrylamido-2-methyl propane sulfonic acid specifically, SSS, sodium vinyl sulfonate, methacrylic acid 3-sulfonic acid propyl ester sylvite or methacrylic acid 3-sulfonic acid propyl ester sodium salt, ALS, methylpropene sodium sulfonate etc.
R
6Be selected from water-soluble double bond containing two degrees of functionality or three-functionality-degree monomer.Include but not limited to N specifically, N-methylene-bisacrylamide, ethoxylated trimethylolpropane triacrylate etc.
Two of the object of the invention provides the preparation method that a kind of preparation contains sulfonic group polymeric particles type catalyst for esterification reaction.This method was divided into for two steps:
The first step of its synthetic method: a certain amount of functional monomer who has sulfonic acid group of weighing.Add initator, addition is that the 3wt% of amount of monomer is to 5wt%.Add crosslinking agent, addition is that amount of monomer changes from 10wt% to 50wt%.Get a certain amount of deionized water, with monomer, crosslinking agent, initator mixes with deionized water.After making it complete dispersing and dissolving, obtain mixed liquor be transparency liquid promptly can be used for second the step.
Can in first step reaction, add pore-foaming agent, addition is 10% to 35% of a deionized water volume, adds in back and the first step after aqueous phase solution mixes and make it complete dispersing and dissolving, obtains mixed liquor and is transparency liquid, promptly can be used for second and goes on foot.
Second step of its synthetic method is: get a certain amount of oil phase, the volume ratio of volume and deionized water changed from 2: 1 to 4.5: 1.Put into reaction vessel, add emulsifying agent, addition is that amount of monomer changes from 8wt% to 15wt%, and sapn series changes from 1: 9 to 9: 1 with the compound emulsifying agent mass ratio of tween series.Be heated to 40 ℃ to 60 ℃ emulsifying agent is melted fully after, add the mixed liquor that obtains after the dissolving in 2, be heated to 80 ℃ to 90 ℃, reacted 4 to 6 hours.Through purifying, drying can obtain the present invention and contain sulfonic polymeric particles type catalyst for esterification reaction after the reaction.
The sulfonic group polymeric particles type catalyst for esterification reaction that contains that the present invention is prepared reaches high catalytic effect through introducing sulfonic acid group; It has the specific area height, the aperture structure homogeneous, and catalytic performance is high; Can repeatedly repeat the excellent characteristics that catalysis is used; And the preparation method is simple, and cost of material is cheap, is fit to suitability for industrialized production.
Description of drawings:
Fig. 1 contains the infrared spectrum of sulfonic group polymeric particles type catalyst for esterification reaction;
Fig. 2 contains sulfonic group polymeric particles type catalyst for esterification reaction and amplifies 200 times of electromicroscopic photographs;
Fig. 3 contains sulfonic group polymeric particles type catalyst for esterification reaction and amplifies 5000 times of electromicroscopic photographs.
The specific embodiment:
Following embodiment can illustrate further characteristics of the present invention, but not limited by these examples.
Embodiment 1
(1) getting 6g SSS monomer adds in the beaker; And adding 0.18g potassium peroxydisulfate initator (3%), the N of 0.6g (10%), N-methylene-bisacrylamide; Add the 20ml deionized water in the beaker that solid is housed; Beaker is placed ultrasonic instrument, and ultrasonic dissolution 30 minutes makes it whole dissolvings.
(2) condensing unit is being housed, agitating device adds 40ml atoleine (with deionized water volume ratio 2: 1) in the reactor of temperature regulating device, and adds the SP-60 of 0.24g, the TW-60 compound emulsifying agent of 0.24g (8%, mass ratio 5: 5).Be heated to 50 ℃, make after emulsifying agent dissolves fully, solution in (1) is poured in the reactor, and temperature is transferred to 90 ℃, react and stop after 4 hours reacting.Solid is taken out, clean 4 times, use washed with de-ionized water again 4 times with absolute ethyl alcohol; Use acetone 2 times afterwards again; Behind the suction filtration with particle in 40 ℃ of vacuum drying ovens, dry and can obtain the faint yellow solid particle in 2 days, be and contain sulfonic polymeric particles type resin catalyst.Product is carried out examination of infrared spectrum, can see that 1184cm is sulfonic characteristic absorption peak, 1126, the 1041cm place is respectively the vibration of face inner frame and the flexural vibrations absworption peak of phenyl ring; 833cm is 1, the characteristic absorption peak of 4-disubstituted benzenes; 3455cm is the characteristic absorption peak of amide groups.Explain and contain groups such as amide groups, sulfonic group, phenyl ring in the polymer that is synthesized, explain that the product of mediating is a target product.
(3) with solid particle be positioned in the 36wt% concentrated hydrochloric acid soak 4-8 hour after, put into after concentrated hydrochloric acid cleaned with deionized water and be added with acrylic acid, n-octyl alcohol, in the reactor of MEHQ, catalyzing propone acid n-octyl synthetic.After reaction finishes, solid catalyst is taken out, after acetone, can carry out repeating the second time catalysis.
After the reaction, get synthetic acrylic acid n-octyl solution with glue head dropper and carry out the gas-chromatography test.Test obtains, and this catalyst repeats 6 times, and Synthesis conversion is respectively 57.5%, 72.2%, and 58%, 71.7%, 43.9%, 38%.
Embodiment 2
(1) getting 6g SSS monomer adds in the beaker; And adding 0.24g potassium peroxydisulfate initator (4%), the N of 1.2g (20%), N-methylene-bisacrylamide; Add the 20ml deionized water in the beaker that solid is housed; Beaker is placed ultrasonic instrument, and ultrasonic dissolution 30 minutes makes it whole dissolvings.
(2) condensing unit is being housed, agitating device adds 90ml atoleine (with the volume ratio of deionized water 4.5: 1) in the reactor of temperature regulating device, and adds the SP-60 of 0.24g, the TW-60 compound emulsifying agent of 0.24g (8%, quality proportioning 5: 5).Be heated to 50 ℃, make after emulsifying agent dissolves fully, solution in (1) is poured in the reactor, and temperature is transferred to 90 ℃, react and stop after 5 hours reacting.Solid is taken out, clean 4 times, use washed with de-ionized water again 4 times with absolute ethyl alcohol; Use acetone 2 times afterwards again; Behind the suction filtration with particle in 40 ℃ of vacuum drying ovens, dry and can obtain the faint yellow solid particle in 2 days, be and contain sulfonic polymeric particles type resin catalyst.
After (3) reaction among the embodiment 1, get synthetic acrylic acid n-octyl solution with glue head dropper and carry out the gas-chromatography test.Test obtains, and this catalyst repeats 11 times, and Synthesis conversion is respectively: 97.9%, 92.2%, 95.6%, 90.7%, 87%, 72.6%, 74.5%, 53%, 52.5%, 51%, 45.5%.
Embodiment 3
(1) gets in 2-acrylamido-2-methyl propane sulfonic acid monomer adding beaker of 6g; And adding 0.3g potassium peroxydisulfate initator (5%), the N of 3.0g (50%), N-methylene-bisacrylamide; Add the 20ml deionized water in the beaker that solid is housed; Beaker is placed ultrasonic instrument, and ultrasonic dissolution 30 minutes makes it whole dissolvings.
(2) condensing unit is being housed, agitating device adds 75ml atoleine (with deionized water volume ratio 3.75: 1) in the reactor of temperature regulating device, and adds the SP-60 of 0.24g, the TW-60 compound emulsifying agent of 0.24g (8%, mass ratio 5: 5).Be heated to 40 ℃, make after emulsifying agent dissolves fully, solution in (1) is poured in the reactor, and temperature is transferred to 90 ℃, react and stop after 4 hours reacting.Solid is taken out, clean 4 times, use washed with de-ionized water again 4 times with absolute ethyl alcohol; Use acetone 2 times afterwards again; Behind the suction filtration with particle in 40 ℃ of vacuum drying ovens, dry and can obtain the faint yellow solid particle in 2 days, be and contain sulfonic polymeric particles type resin catalyst.
After (3) reaction among the embodiment 1, get synthetic acrylic acid n-octyl solution with glue head dropper and carry out the gas-chromatography test.Test obtains, and after this catalyst repeated 8 times, catalytic effect was lower, no longer repeated catalysis.Synthesis conversion is respectively: 68.3%, 65%, 59.8%, 54.7%, 50.1%, 43.2%, 38.5%, 35.4%.
Embodiment 4
(1) gets in 2-acrylamido-2-methyl propane sulfonic acid monomer adding beaker of 6g, and add 0.24g potassium peroxydisulfate initator, the N of 0.6g (10%); The N-methylene-bisacrylamide; The 2ml n-butanol is pore-foaming agent (being the 10wt% of deionized water), adds the 20ml deionized water again in beaker, and beaker is placed ultrasonic instrument; Ultrasonic dissolution 30 minutes makes it whole dissolvings.
(2) condensing unit is being housed, agitating device adds the 75ml atoleine in the reactor of temperature regulating device, and adds the SP-60 of 0.24g, the TW-60 compound emulsifying agent of 0.24g (8%, proportioning 5: 5).Be heated to 60 ℃, make after emulsifying agent dissolves fully, solution in (1) is poured in the reactor, and temperature is transferred to 90 ℃, react and stop after 5 hours reacting.Solid is taken out, clean 4 times, use washed with de-ionized water again 4 times with absolute ethyl alcohol; Use acetone 2 times afterwards again; Behind the suction filtration with particle in 40 ℃ of vacuum drying ovens, dry and can obtain the faint yellow solid particle in 2 days, be and contain sulfonic polymeric particles type resin catalyst.
After (3) reaction among the embodiment 1, get synthetic acrylic acid n-octyl solution with glue head dropper and carry out the gas-chromatography test.Test obtains, and this catalyst repeats catalysis 6 times, and Synthesis conversion is respectively: 77.5%, 84.2%, 80.7%, 74.3%, 68.8%, 60.5%.
Embodiment 5
(1) gets in 2-acrylamido-2-methyl propane sulfonic acid monomer adding beaker of 3g SSS monomer and 3g, and add 0.24g potassium peroxydisulfate initator, the N of 0.6g (10%); The N-methylene-bisacrylamide; The 7ml n-butanol is pore-foaming agent (35wt% of deionized water), adds the 20ml deionized water again in beaker, and beaker is placed ultrasonic instrument; Ultrasonic dissolution 30 minutes makes it whole dissolvings.
(2) condensing unit is being housed, agitating device adds the 75ml atoleine in the reactor of temperature regulating device, and adds the SP-60 of 0.06g, the TW-60 compound emulsifying agent of 0.54g (10%, proportioning is 1: 9).Be heated to 50 ℃, make after emulsifying agent dissolves fully, solution in (1) is poured in the reactor, and temperature is transferred to 90 ℃, react and stop after 4 hours reacting.Solid is taken out, clean 4 times, use washed with de-ionized water again 4 times with absolute ethyl alcohol; Use acetone 2 times afterwards again; Behind the suction filtration with particle in 40 ℃ of vacuum drying ovens, dry and can obtain the faint yellow solid particle in 2 days, be and contain sulfonic polymeric particles type resin catalyst.
After (3) reaction among the embodiment 1, get synthetic acrylic acid n-octyl solution with glue head dropper and carry out the gas-chromatography test.Test obtains, and this catalyst repeats catalysis 6 times, and Synthesis conversion is respectively 62.3%, 70.4%, and 61.2%, 55.6%, 49.5%, 43.2%.
Embodiment 6
(1) gets in the sodium vinyl sulfonate monomer adding beaker of 3g SSS monomer and 3g; And adding 0.24g potassium peroxydisulfate initator, the N of 0.6g (10%), N-methylene-bisacrylamide; Add the 20ml deionized water again in beaker; Beaker is placed ultrasonic instrument, and ultrasonic dissolution 30 minutes makes it whole dissolvings.
(2) condensing unit is being housed, agitating device adds the 75ml atoleine in the reactor of temperature regulating device, and adds the SP-60 of 0.54g, the TW-60 compound emulsifying agent of 0.06g (10%, proportioning is 9: 1).Be heated to 50 ℃, make after emulsifying agent dissolves fully, solution in (1) is poured in the reactor, and temperature is transferred to 90 ℃, react and stop after 5 hours reacting.Solid is taken out, clean 4 times, use washed with de-ionized water again 4 times with absolute ethyl alcohol; Use acetone 2 times afterwards again; Behind the suction filtration with particle in 40 ℃ of vacuum drying ovens, dry and can obtain the faint yellow solid particle in 2 days, be and contain sulfonic polymeric particles type resin catalyst.
After (3) reaction among the embodiment 1, get synthetic acrylic acid n-octyl solution with glue head dropper and carry out the gas-chromatography test.Test obtains, and this catalyst repeats catalysis 6 times, and Synthesis conversion is respectively 54.3%, 50.0%, and 47.6%, 43.3%, 37.5%, 33.4%.
Embodiment 7
(1) gets 6g sodium vinyl sulfonate monomer and add in the beaker, and add 0.24g potassium peroxydisulfate initator, the N of 0.6g (10%); The N-methylene-bisacrylamide adds the 20ml deionized water again in beaker, and beaker is placed ultrasonic instrument; Ultrasonic dissolution 30 minutes makes it whole dissolvings.
(2) condensing unit is being housed, agitating device adds the 75ml atoleine in the reactor of temperature regulating device, and adds the SP-60 of 0.45g, the TW-60 compound emulsifying agent of 0.45g (15%, proportioning is 5: 5).Be heated to 50 ℃, make after emulsifying agent dissolves fully, solution in (1) is poured in the reactor, and temperature is transferred to 90 ℃, react and stop after 5 hours reacting.Solid is taken out, clean 4 times, use washed with de-ionized water again 4 times with absolute ethyl alcohol; Use acetone 2 times afterwards again; Behind the suction filtration with particle in 40 ℃ of vacuum drying ovens, dry and can obtain the faint yellow solid particle in 2 days, be and contain sulfonic polymeric particles type resin catalyst.
After (3) reaction among the embodiment 1, get synthetic acrylic acid n-octyl solution with glue head dropper and carry out the gas-chromatography test.Test obtains, and this catalyst can repeat catalysis 4 times, and Synthesis conversion is respectively 55.4%, 49.8%, and 43.5%, 39.8%.
Claims (5)
1. contain sulfonic group polymeric particles type catalyst for esterification reaction, it is characterized in that this catalyst structure formula is shown in (I):
N wherein, m is the integer greater than 1, can be identical or different;
R
1Be hydrogen atom or methyl;
R
2, R
3, R
4, R
5Be selected from and contain different phenyl ring or amide groups or different carbon chain lengths alkyl group,
R
2, R
3, R
4, R
5Identical or different; R
6Be selected from water-soluble double bond containing two degrees of functionality or three-functionality-degree monomer.
2. sulfonic polymeric particles shape catalyst for esterification reaction according to claim 1 is characterized in that: R
2, R
3, R
4, R
5Be 2-acrylamido-2-methyl propane sulfonic acid, SSS, sodium vinyl sulfonate, methacrylic acid 3-sulfonic acid propyl ester sylvite or methacrylic acid 3-sulfonic acid propyl ester sodium salt, ALS or methylpropene sodium sulfonate.
3. sulfonic polymeric particles shape catalyst for esterification reaction according to claim 1 is characterized in that: R
6Be N, N-methylene-bisacrylamide or ethoxylated trimethylolpropane triacrylate.
4. the preparation method of sulfonic polymeric particles shape catalyst for esterification reaction according to claim 1 is characterized in that step is following:
The first step: weighing has the functional monomer of sulfonic acid group; Add initator again, addition is that the 3wt% of amount of monomer is to 5wt%; Add crosslinking agent, addition is that amount of monomer changes from 10wt% to 50wt%; Remove ionized water, with monomer, crosslinking agent, initator mixes with deionized water, behind the dispersing and dissolving, obtains mixed liquor and is transparency liquid fully;
Second step: get oil phase, the volume ratio of oil phase volume and deionized water changed from 2: 1 to 4.5: 1; Put into reaction vessel, add compound emulsifying agent, addition is that amount of monomer changes from 8wt% to 15wt%, and above-mentioned compound emulsifying agent is made up of sapn series and tween series, and sapn series changes from 1: 9 to 9: 1 with the mass ratio of tween series;
Be heated to 40 ℃ to 60 ℃ compound emulsifying agent is melted fully after, add in the above-mentioned first step mixed liquor that obtains after the dissolving, be heated to 80 ℃ to 90 ℃, reacted 4 to 6 hours; Through purifying, drying can obtain containing sulfonic polymeric particles type catalyst for esterification reaction after the reaction.
5. the preparation method of sulfonic polymeric particles shape catalyst for esterification reaction according to claim 1 is characterized in that step is following: in first step reaction, also add pore-foaming agent, addition is 10% to 35% of a deionized water volume.
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| CN104119467A (en) * | 2014-07-10 | 2014-10-29 | 上海应用技术学院 | Strong-acid cation exchange resin and preparing method thereof |
| CN109876858A (en) * | 2019-01-14 | 2019-06-14 | 广东博兴新材料科技有限公司 | One kind preparation method of (methyl) acrylate substance and the application of 2- acrylamide-2-methyl propane sulfonic |
| CN110975935A (en) * | 2019-12-25 | 2020-04-10 | 武汉工程大学 | Preparation method and application of solid acid catalyst |
| CN114426486A (en) * | 2020-09-23 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methyl methacrylate and supported catalyst |
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| CN114426486A (en) * | 2020-09-23 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methyl methacrylate and supported catalyst |
| CN114426486B (en) * | 2020-09-23 | 2024-02-13 | 中国石油化工股份有限公司 | Method for preparing methyl methacrylate and supported catalyst |
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