CN101724148A - Preparation method of macromonomer - Google Patents
Preparation method of macromonomer Download PDFInfo
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- CN101724148A CN101724148A CN200910312506A CN200910312506A CN101724148A CN 101724148 A CN101724148 A CN 101724148A CN 200910312506 A CN200910312506 A CN 200910312506A CN 200910312506 A CN200910312506 A CN 200910312506A CN 101724148 A CN101724148 A CN 101724148A
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- polyoxyethylene glycol
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Abstract
The invention discloses a preparation method of a macromonomer, belonging to the technical field of water treatment. The method comprises the following steps of: (1), taking acid and taking polyethylene glycol simultaneously, wherein the acid is crylic acid or methacrylic acid; and (2), under the condition of the existences of a polymerization inhibitor and a catalyst, adjusting reaction temperature to be 100-150 DEG C and leading nitrogen to enable the raw materials taken from the step one to be subjected to esterification reaction so as to obtain the macromonomer by collecting a reaction product. In the technical scheme of the invention, no organic solvent is used so that the cost is reduced; and the temperature is raised during preparation and the nitrogen is led simultaneously, thereby being beneficial to discharging water vapor and quickening the progress of the esterification reaction.
Description
Technical field
The present invention relates to a kind of preparation method of water-treatment technology field, specifically is a kind of big monomeric preparation method.
Background technology
Along with the fast development of economic construction, environmental problem has been subjected to the whole world and has paid close attention to, and underground water occupies an important position as important water resources.In the available Freshwater resources in the whole world, underground water accounts for 95%.China's town water total amount is heavy, and underground water accounts for 30%.North China, city, northwest utilize phreatic ratio respectively up to 72% and 66%.Nearly 50% urban groundwater suffers pollution in various degree at present.Pollutent has heavy metal, metalloid element (as the arsenic compounds), poisonous element, organism and nitrate etc., and majority is a combined pollution.How to remove phreatic heavy metal ion, metalloid element and poisonous element, for the water safety that ensures people's lives, uplifting the people's living standard has important practical significance.At present, the effective means of removing in the underground water of heavy metal ion, metalloid element and poisonous element is to pass through fractionation by adsorption, preparation adsorption efficiency excellence and the reusable sorbing material of energy be to improve ground water cleaning usefulness, reclaim the basic assurance of heavy metal ions in wastewater.
Find through literature search prior art, (Qin Chaoguo such as Qin Chaoguo, Li Xiang, the study on the synthesis of methacrylic acid polyethylene glycol (400) monoesters, the Guangdong chemical industry, 2007, No.8, p16) propose to adopt the mode that vacuumizes to remove generation water, but also a large amount of eliminatings reactant methacrylic acid (vinylformic acid).Also can add lower boiling band water solvent in the reaction system and carry out esterification, make the water of solvent and generation form azeotrope, the maintenance system is in boiling state, not only helps uniformly transfer heat, and can take away the water molecules of generation, the transformation efficiency of enhance esterification, but the amount of solvent is difficult to hold, if the consumption of solvent is too many, then can causes reactant concn to descend the reaction times is prolonged, as consumption very little, can not remove water molecules well again; In addition, solvent must remove and reclaim by underpressure distillation after esterification, and this has not only increased the production technique cost, also causes environmental problem easily.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of big monomeric preparation method is provided.Technical scheme of the present invention has not with an organic solvent reduced cost; Improve temperature in the preparation process, fed nitrogen simultaneously, helped the discharge of water vapor, and accelerated the process of esterification.
The present invention realizes by following technical scheme, the present invention includes following steps:
Step 1 is got acid, simultaneously taking polyethylene glycol;
Described acid is acrylic or methacrylic acid;
Step 2, under the condition of stopper and catalyzer existence, adjusting temperature of reaction is 100～150 ℃, feeds nitrogen, makes raw material that step 1 is got carry out esterification, collecting reaction product obtains big monomer.
In the step 1, described polyoxyethylene glycol is PEG-400, PEG-600, PEG-1000 or PEG-2000.
In the step 1, in molar ratio, polyoxyethylene glycol is 1 with the ratio of acid: (1～10).
In the step 1, in molar ratio, polyoxyethylene glycol is 1 with the ratio of acid: (1～6).
In the step 2, described stopper is one or more the mixing in the following combination: Resorcinol, phenothiazine, para benzoquinone, toluhydroquinone and 2,5 di tert butyl hydroquinone.
In the step 2, described stopper is one or more the mixing in the following combination: Resorcinol, para benzoquinone and phenothiazine.
In the step 2, the quality of described stopper is 0.3～3% of a sour quality.
In the step 2, described catalyzer is one or more the mixing in the following combination: sulfuric acid, hydrochloric acid, Phenylsulfonic acid and tosic acid.
In the step 2, described catalyzer is one or more the mixing in the following combination: sulfuric acid, Phenylsulfonic acid and tosic acid.
In the step 2, the quality of described catalyzer is to get acid and 1～5% of polyoxyethylene glycol total mass in the step 1.
Among the present invention, esterification usually needs acid, alkali as catalyzer, could carry out smoothly, adds catalyzer, preferred 1～3% according to 1～5% of reaction raw materials (acrylic or methacrylic acid, and polyoxyethylene glycol) total mass usually.Because vinylformic acid and methacrylic acid are the vinyl monomers that very easily carries out thermopolymerization,,, influence the preparation and the performance of follow-up sorbing material to prevent their thermopolymerizations in esterification process so in preparation process, need to add a certain amount of stopper; Usually, add stopper, preferred 0.5～1.5% according to 0.3～3% of acrylic or methacrylic acid weight.Esterification is a reaction (equilibrium constant K is about 4) that the equilibrium constant is lower, guarantee that esterification can obtain meeting the requirements of esterification yield in the suitable reaction times, must select suitable temperature of reaction and the by product H that removes generation
2The O molecule makes balance move to helping the esterification direction.Temperature of reaction of the present invention can make the H of generation
2O is transformed into steam, can utilize nitrogen that steam is blown the discharge reaction system simultaneously, at utmost reduces the loss of vinylformic acid, methacrylic acid.
Compared with prior art, the present invention has following beneficial effect: not with an organic solvent, eliminated their disadvantageous effects to environment in the technical scheme of the present invention, simultaneously without solvent recovery unit, reduced unnecessary investment; In preparation process, owing to improved temperature of reaction, make reaction product water be vaporizated into steam, after guaranteeing to feed nitrogen, utilize water vapor to be blown out with nitrogen, break away from reaction system, the water vapor condensation that contains the methacrylic acid of minute quantity reclaims; Simultaneously, increase substantially the temperature of reaction system, accelerated the process of esterification greatly.
Embodiment 1
The single end-blocking of methacrylic acid polyethylene glycol-400 is big monomeric synthetic
Get 1mol polyoxyethylene glycol-400, the 1.1mol methacrylic acid; Polyoxyethylene glycol is added in the four-hole boiling flask, feed nitrogen, be warming up to 85 ℃, 3% the Resorcinol that adds the methacrylic acid quality is as stopper; 2% the concentrated hydrochloric acid that adds methacrylic acid and polyoxyethylene glycol-400 total mass is as catalyzer;
In above-mentioned system, drip the methacrylic acid of 0.1mol earlier fast, after dropwising, take a sample, measure the basic acid number of system with the method for acid base titration; And then drip remaining methacrylic acid fast, and after dropwising, take a sample with the method for same acid base titration, measure the initial acid value of system; Be warming up to 100 ℃, measured the acid number of primary first-order equation process in per 2 hours, when acid number drops to basic acid number, can assert polyoxyethylene glycol in the esterification-400 esterified half, after esterification finished, products therefrom was the big monomer of methacrylic acid list end-blocking polyoxyethylene glycol-400.Through computational analysis, actual esterification yield can reach more than 90%, can be used as the sorbent material of underground water heavy metal, metalloid element and poisonous element polymeric adsorbent.
Embodiment 2
Methacrylic acid list end-blocking polyoxyethylene glycol-1000 is big monomeric synthetic
Polyoxyethylene glycol-1000 after 60 ℃ of thawings, is taken by weighing 0.4mol and joins in the four-hole boiling flask, take by weighing the 0.48mol methacrylic acid.Polyoxyethylene glycol is under the liquid state, feeds nitrogen, is warming up to 85 ℃, and 0.3% phenothiazine that adds the methacrylic acid quality is as stopper; 1% the phenylformic acid that adds methacrylic acid and polyoxyethylene glycol-1000 total mass is as catalyzer;
At first in above-mentioned system, drip the methacrylic acid of 0.08mol fast, after dropwising, the sampling method of acid base titration, the basic acid number of mensuration system; Drip the methacrylic acid of 0.4mol then fast, after dropwising, take a sample, measure the initial acid value of system with the method for same acid base titration; System is warming up to 125 ℃, measured the acid number of primary first-order equation process in per 2 hours, when acid number drops to basic acid number, can assert esterification proceed to polyoxyethylene glycol-1000 esterified half, esterification finishes, and products therefrom is the big monomer of methacrylic acid list end-blocking polyoxyethylene glycol-1000.Through computational analysis, actual esterification yield can reach more than 90%, can be used as the sorbent material of underground water heavy metal, metalloid element and poisonous element polymeric adsorbent.
Embodiment 3
The two end-blocking polyoxyethylene glycol-600 of vinylformic acid are big monomeric synthetic
Take by weighing 0.7mol polyoxyethylene glycol-600 and join in the four-hole boiling flask, take by weighing the vinylformic acid of 1.575mol.Feed nitrogen, be warming up to 85 ℃, 1.2% the para benzoquinone that adds the vinylformic acid quality is as stopper; 5% the tosic acid that adds vinylformic acid and polyoxyethylene glycol-600 total mass is as catalyzer;
At first in above-mentioned system, drip the vinylformic acid of 0.175mol fast, after dropwising, the sampling method of acid base titration, the basic acid number of mensuration system; And then drip the vinylformic acid of 1.4mol fast, after dropwising, sampling is measured the initial acid value of system with the method for acid base titration; System was warming up to 150 ℃, measured the acid number of primary first-order equation process every 2 hours, when acid number drops to basic acid number, assert that esterification finishes, and products therefrom is the two end-blocking polyoxyethylene glycol-600 of vinylformic acid monomer greatly.Analyze as calculated, actual esterification yield can reach more than 90%, can be used as the linking agent of underground water heavy metal, metalloid element and poisonous element polymeric adsorbent.
Embodiment 4
Methacrylic acid list end-blocking polyoxyethylene glycol-1000 is big monomeric synthetic
Polyoxyethylene glycol-1000 after 60 ℃ of thawings, is taken by weighing 0.4mol and joins in the four-hole boiling flask, add the 0.4mol methacrylic acid.Polyoxyethylene glycol is under the liquid state, feeds nitrogen, is warming up to 85 ℃, and 0.3% para benzoquinone of adding methacrylic acid quality and the mixture (mass ratio 1: 1) of Resorcinol are as stopper; 1% the acid that adds methacrylic acid and polyoxyethylene glycol-1000 total mass is as catalyzer, and to be 98% the vitriol oil by tosic acid and massfraction by mass ratio=1: 4 mix obtains in described acid; The tosic acid particle that at first takes by weighing metering joins in the polyoxyethylene glycol, and then adds 98% the vitriol oil of metering.
After having added catalyzer to reaction system, the basic acid number of system is measured in sampling with the method for acid base titration; Drip the methacrylic acid of 0.4mol then fast, after dropwising, the initial acid value of sampling and measuring system.System is warming up to 120 ℃, measured the acid number of primary first-order equation process every 2 hours, when acid number drops to basic acid number, can assert esterification proceed to polyoxyethylene glycol-1000 esterified half, assert that esterification finishes, products therefrom is the big monomer of methacrylic acid list end-blocking polyoxyethylene glycol-1000.Through computational analysis, actual esterification yield can reach more than 90%, can be used as the sorbent material of underground water heavy metal, metalloid element and poisonous element polymeric adsorbent.
Embodiment 5
Methacrylic acid list end-blocking polyoxyethylene glycol-2000 is big monomeric synthetic
Polyoxyethylene glycol-2000 after 70 ℃ of thawings, is taken by weighing 0.2mol and joins in the four-hole boiling flask, add the 2mol methacrylic acid.Polyoxyethylene glycol is under the liquid state, feeds nitrogen, is warming up to 85 ℃, and 0.5% para benzoquinone of adding methacrylic acid quality and the mixture (mass ratio 1: 3) of phenothiazine are as stopper; 1% the acid that adds methacrylic acid and polyoxyethylene glycol-2000 total mass is as catalyzer, and to be 98% the vitriol oil by tosic acid and massfraction by mass ratio=2: 1 mix obtains in described acid; The tosic acid particle that at first takes by weighing metering joins in the polyoxyethylene glycol, and then adds 98% the vitriol oil of metering.
Add catalyzer to reaction system, at first in above-mentioned system, dripping the methacrylic acid of 0.2mol fast, after dropwising, the sampling method of acid base titration, the basic acid number of mensuration system; Drip the methacrylic acid of 1.8mol then fast, after dropwising, the initial acid value of sampling and measuring system.System is warming up to 130 ℃, measured the acid number of primary first-order equation process every 2 hours, when acid number drops to basic acid number, can assert esterification proceed to polyoxyethylene glycol-2000 esterified half, assert that esterification finishes, products therefrom is the big monomer of methacrylic acid list end-blocking polyoxyethylene glycol-2000.Analyze as calculated, actual esterification yield can reach more than 90%, can be used as the sorbent material of underground water heavy metal, metalloid element and poisonous element polymeric adsorbent.
Embodiment 6
The two end-blocking polyoxyethylene glycol-600 of vinylformic acid are big monomeric synthetic
Take by weighing 0.7mol polyoxyethylene glycol-600 and join in the four-hole boiling flask, take by weighing 4.2mol vinylformic acid.Polyoxyethylene glycol is under the liquid state, feeds nitrogen, is warming up to 85 ℃, and the mixture (mass ratio 1: 1: 3) of 0.8% para benzoquinone, Resorcinol and the phenothiazine of adding vinylformic acid quality is as stopper; The acid that adds vinylformic acid and polyoxyethylene glycol-600 total mass 1.5% is as catalyzer, and described acid is obtained by mass ratio=mixing in 1: 1 by Phenylsulfonic acid and tosic acid; The Phenylsulfonic acid and the tosic acid particle that take by weighing metering join in the polyoxyethylene glycol.
At first in above-mentioned system, drip the vinylformic acid of 2.8mol fast, after dropwising, the sampling method of acid base titration, the basic acid number of mensuration system; Drip the vinylformic acid of 1.4mol then fast, after dropwising, the initial acid value of sampling and measuring system.System was warming up to 135 ℃, measured the acid number of primary first-order equation process every 2 hours, when acid number drops to basic acid number, assert that esterification finishes, and products therefrom is the two end-blocking polyoxyethylene glycol-600 of vinylformic acid monomer greatly.Through computational analysis, actual esterification yield can reach more than 90%, can be used as the linking agent of underground water heavy metal, metalloid element and poisonous element polymeric adsorbent.
Claims (10)
1. one kind big monomeric preparation method is characterized in that, comprises the steps:
Step 1 is got acid, simultaneously taking polyethylene glycol;
Described acid is acrylic or methacrylic acid;
Step 2, under the condition of stopper and catalyzer existence, adjusting temperature of reaction is 100～150 ℃, feeds nitrogen, makes raw material that step 1 is got carry out esterification, collecting reaction product obtains big monomer.
2. big monomeric preparation method according to claim 1 is characterized in that, in the step 1, described polyoxyethylene glycol is PEG-400, PEG-600, PEG-1000 or PEG-2000.
3. big monomeric preparation method according to claim 1 is characterized in that, in the step 1, in molar ratio, polyoxyethylene glycol is 1 with the ratio of acid: (1～10).
4. big monomeric preparation method according to claim 3 is characterized in that, in the step 1, in molar ratio, polyoxyethylene glycol is 1 with the ratio of acid: (1～6).
5. big monomeric preparation method according to claim 1 is characterized in that, in the step 2, described stopper is one or more the mixing in the following combination: Resorcinol, phenothiazine, para benzoquinone, toluhydroquinone and 2,5 di tert butyl hydroquinone.
6. big monomeric preparation method according to claim 1 is characterized in that, in the step 2, described stopper is one or more the mixing in the following combination: Resorcinol, para benzoquinone and phenothiazine.
7. big monomeric preparation method according to claim 1 is characterized in that, in the step 2, the quality of described stopper is 0.3～3% of a sour quality.
8. big monomeric preparation method according to claim 1 is characterized in that, in the step 2, described catalyzer is one or more the mixing in the following combination: sulfuric acid, hydrochloric acid, Phenylsulfonic acid and tosic acid.
9. big monomeric preparation method according to claim 1 is characterized in that, in the step 2, described catalyzer is one or more the mixing in the following combination: sulfuric acid, phenylformic acid and tosic acid.
10. big monomeric preparation method according to claim 1 is characterized in that in the step 2, and the quality of described catalyzer is to get acid and 1～5% of polyoxyethylene glycol total mass in the step 1.
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| CN200910312506A CN101724148A (en) | 2009-12-29 | 2009-12-29 | Preparation method of macromonomer |
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| CN200910312506A CN101724148A (en) | 2009-12-29 | 2009-12-29 | Preparation method of macromonomer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271906A (en) * | 2015-11-05 | 2016-01-27 | 江苏苏博特新材料股份有限公司 | Organic corrosion and rust inhibitor and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271906A (en) * | 2015-11-05 | 2016-01-27 | 江苏苏博特新材料股份有限公司 | Organic corrosion and rust inhibitor and preparation method thereof |
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Open date: 20100609 |