CN115745813A - Preparation method of methacryloyloxyethyl dimethyl benzyl ammonium chloride solution - Google Patents
Preparation method of methacryloyloxyethyl dimethyl benzyl ammonium chloride solution Download PDFInfo
- Publication number
- CN115745813A CN115745813A CN202211317771.4A CN202211317771A CN115745813A CN 115745813 A CN115745813 A CN 115745813A CN 202211317771 A CN202211317771 A CN 202211317771A CN 115745813 A CN115745813 A CN 115745813A
- Authority
- CN
- China
- Prior art keywords
- ammonium chloride
- chloride solution
- weight
- parts
- deionized water
- 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.)
- Pending
Links
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002738 chelating agent Substances 0.000 claims abstract description 19
- 239000003112 inhibitor Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000009849 vacuum degassing Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- HHYHXLLRSHJLTK-UHFFFAOYSA-N C=C.[Na].[Na].[Na].[Na] Chemical group C=C.[Na].[Na].[Na].[Na] HHYHXLLRSHJLTK-UHFFFAOYSA-N 0.000 claims 1
- VXLCKSFMONBCLQ-UHFFFAOYSA-N [Na]CC[Na] Chemical group [Na]CC[Na] VXLCKSFMONBCLQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 238000001514 detection method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000004321 preservation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 2
- KFDNQUWMBLVQNB-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KFDNQUWMBLVQNB-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution, belonging to the technical field of chemical industry. The preparation method comprises the following steps: adding 30-35 parts by weight of dimethylaminoethyl methacrylate into a reaction kettle, then adding a chelating agent, stirring, and heating to 35-55 ℃; dripping 7.0-10.0 weight parts of benzyl chloride once, then adding 3.0-5.0 weight parts of deionized water, and reacting for 10-20 min; 8.5 to 12.0 weight parts of benzyl chloride is dripped for the second time to react for 15 to 30min, and then 8.0 to 10.0 weight parts of deionized water is added; dripping 6.5-9.0 parts by weight of benzyl chloride for three times, reacting for 60-180 min, adding 23-30 parts by weight of deionized water, adding a polymerization inhibitor, stirring, and vacuum degassing for 60-120 min to obtain the methacryloyloxyethyl dimethyl benzyl ammonium chloride solution. The method is mainly used for preparing the methacryloyloxyethyl dimethyl benzyl ammonium chloride solution, is convenient to implement, saves energy, protects the environment, and has low acid value and strong stability of the product.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution.
Background
Methacryloyloxyethyl dimethyl benzyl ammonium chloride is one of the most practical cationic monomers at present, and the molecular structure of the methacryloyloxyethyl dimethyl benzyl ammonium chloride simultaneously contains a polymerizable double bond, an easily degradable ester functional group, a hydrophilic quaternary ammonium alkyl group and an oleophilic benzyl group. The homopolymer and copolymer macromolecules generated by polymerization have the advantages of high positive charge density, good water solubility, high efficiency, no toxicity and the like, the introduction of the benzene ring enables the polymer to be easily sulfonated, and the sulfonated polymer can be widely applied to the fields of oil exploitation, papermaking, coal flotation, water treatment and the like.
CN1283619C discloses a method for preparing an aqueous solution of (meth) acryloyloxyethyldimethylbenzyl ammonium chloride, which comprises the steps of preparing an aqueous solution of methacryloyloxyethyldimethylbenzyl ammonium chloride by reacting dimethylaminoethyl methacrylate with benzyl chloride in the presence of water, adding the aqueous solution of methacryloyloxyethyldimethylbenzyl ammonium chloride, and then simultaneously dropwise adding dimethylaminoethyl methacrylate, benzyl chloride and water. However, in the presence of water, dimethylaminoethyl methacrylate is easily hydrolyzed when meeting water to generate acrylic acid, so that the acid value of the finished solution is reduced, the stability is deteriorated, and the positive charge density, the water solubility and other properties of the subsequently synthesized cationic polyacrylamide are affected.
Disclosure of Invention
The invention provides a preparation method of a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution, which can reduce hydrolysis of dimethylaminoethyl methacrylate, and the prepared methacryloyloxyethyl dimethyl benzyl ammonium chloride solution has low acid value and good stability and meets the requirements of environmental protection.
The invention provides a preparation method of a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution, which comprises the following steps:
adding 30-35 parts by weight of dimethylaminoethyl methacrylate into a reaction kettle, then adding a chelating agent, stirring, and heating to 35-55 ℃;
dripping 7.0-10.0 weight parts of benzyl chloride once, then adding 3.0-5.0 weight parts of deionized water, and reacting for 10-20 min;
8.5 to 12.0 weight parts of benzyl chloride is dripped for the second time to react for 15 to 30min, and then 8.0 to 10.0 weight parts of deionized water is added;
dropwise adding 6.5-9.0 parts by weight of benzyl chloride for three times, reacting for 60-180 min, adding 23-30 parts by weight of deionized water, adding a polymerization inhibitor, stirring, and vacuum degassing for 60-120 min to obtain a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution;
wherein the sum of the parts by weight of the dimethylaminoethyl methacrylate, the benzyl chloride and the deionized water is 100.
Further, the chelating agent comprises at least one of disodium ethylene diamine tetraacetic acid and tetrasodium ethylene diamine tetraacetic acid.
Furthermore, the content of the chelating agent in the methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 10-50 ppm.
Further, the polymerization inhibitor is p-hydroxyanisole.
Furthermore, the content of the polymerization inhibitor in the methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 500-1000 ppm.
Furthermore, the pressure of vacuum degassing is-0.02 to-0.09 KMP, and the temperature of vacuum degassing is 40 to 55 ℃.
Further, the reaction temperature throughout the process was controlled to 35 to 55 ℃.
Furthermore, the reaction kettle is an anhydrous reaction kettle in the kettle.
The invention has the following advantages:
the preparation method of the methacryloyloxyethyl dimethylbenzyl ammonium chloride solution provided by the invention ensures that the reaction starts in an anhydrous environment, the benzyl chloride and water are alternately dripped in the reaction process, the addition amount of water in each addition process is convenient to control, the phenomenon that the added water does not participate in the reaction in time to hydrolyze dimethylaminoethyl methacrylate into acrylic acid is avoided, the acid value of a finished product is further reduced, and the shelf life of the obtained methacryloyloxyethyl dimethylbenzyl ammonium chloride solution can be prolonged to 6-12 months. Therefore, the method is convenient to implement, low in energy consumption, energy-saving and environment-friendly, and the obtained product is low in acid value and high in stability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
An embodiment of the invention provides a preparation method of a methacryloyloxyethyl dimethylbenzyl ammonium chloride solution, which comprises the following steps:
adding 30-35 parts by weight of dimethylaminoethyl methacrylate into a reaction kettle, then adding a chelating agent, stirring, and heating to 35-55 ℃;
dripping 7.0-10.0 weight parts of benzyl chloride once, then adding 3.0-5.0 weight parts of deionized water, and reacting for 10-20 min;
8.5 to 12.0 weight parts of benzyl chloride is dripped for the second time to react for 15 to 30min, and then 8.0 to 10.0 weight parts of deionized water is added;
dropwise adding 6.5-9.0 parts by weight of benzyl chloride for three times, reacting for 60-180 min, adding 23-30 parts by weight of deionized water, adding a polymerization inhibitor, stirring, and vacuum degassing for 60-120 min to obtain a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution;
wherein the sum of the parts by weight of the dimethylaminoethyl methacrylate, the benzyl chloride and the deionized water is 100.
The preparation method of the methacryloyloxyethyl dimethylbenzyl ammonium chloride solution provided by the embodiment of the invention is carried out in an anhydrous environment at the beginning of the reaction, and benzyl chloride and water are alternately dripped in the reaction process, so that the problem that dimethylaminoethyl methacrylate is hydrolyzed into acrylic acid due to untimely reaction of the added water can be effectively avoided, the acid value of a finished product is further reduced, and the acid value can be prolonged to 6-12 months. Therefore, the method is convenient to implement, low in energy consumption, energy-saving and environment-friendly, the obtained product is low in acid value and high in stability, and the method is beneficial to the subsequent preparation of polymers.
In an embodiment of the present invention, the chelating agent includes at least one of disodium ethylenediaminetetraacetic acid and tetrasodium ethylenediaminetetraacetic acid. The chelating agent in the embodiment of the invention can be used for chelating metal ions generated in the reaction kettle, so that the effects of the reaction and the reaction product are prevented from being influenced.
In one embodiment of the invention, the content of the chelating agent in the methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 10-50 ppm. The chelating agent is added in a small amount, and therefore, the proportion of the chelating agent in the system is calculated in ppm.
In an embodiment of the invention, the polymerization inhibitor is p-hydroxyanisole. According to the embodiment of the invention, the self-polymerization of the monomer can be effectively avoided by adding a small amount of polymerization inhibitor. The polymerization inhibitor is added in a small amount, and therefore, the proportion of the polymerization inhibitor in the system is calculated in ppm. Preferably, the content of the polymerization inhibitor in the methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 500-1000 ppm.
In one embodiment of the invention, the pressure of vacuum degassing is-0.02 to-0.09 KMP, and the temperature of vacuum degassing is 40 to 55 ℃. In the embodiment of the invention, vacuum degassing is adopted in the reaction process to remove residual benzyl alcohol and benzyl chloride and remove odor, so that the acid value is reduced, the finished product is more stable, and the storage period is longer.
In one embodiment of the invention, the reaction temperature in the whole process is controlled to be 35-55 ℃.
In an embodiment of the invention, the reaction kettle is a reaction kettle without water in the kettle. Further, the whole reaction process is carried out in a stainless steel normal pressure reaction kettle which is provided with a stirrer and can control the temperature, and nitrogen is used for replacement.
Example 1Preparation of methacryloyloxyethyl dimethylbenzyl ammonium chloride solutionThe method comprises the following steps:
ensuring that a reaction kettle is clean and anhydrous, adding 32.5wt% of dimethylaminoethyl methacrylate and 10ppm of chelating agent into the reaction kettle according to the mass fraction, starting stirring and heating, heating to 40 ℃, starting dropwise adding 8.5wt% of benzyl chloride, adding 4.5wt% of deionized water after dropwise adding, and reacting for 15min; continuously dropwise adding 9.5wt% of benzyl chloride, finishing the reaction for 20min after dropwise adding, and then adding 9.5wt% of deionized water; continuously dropwise adding 7.5wt% of benzyl chloride, and finishing the heat preservation reaction for 120min; the temperature of the whole reaction process is controlled to be 35-45 ℃; and after the heat preservation is finished, continuously adding 28.0wt% of deionized water and 500ppm of polymerization inhibitor, uniformly stirring, and performing vacuum degassing (-0.02-0.09KMP, 45 ℃) for 90min to obtain the methacryloyloxyethyl dimethyl benzyl ammonium chloride solution.
And (3) detecting the obtained product, wherein the detection method comprises the following steps:
the color was measured according to the method specified in GB/T3143-1982.
The content is measured by taking potassium chromate as an indicator and titrating with silver nitrate standard titration solution.
The acid value was determined by titration with standard sodium hydroxide titration solution using phenolphthalein as an indicator.
The pH was measured using a pH meter.
Through detection, the content of the obtained methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 60.1%, the pH value is 6.18, the acid value is 0.086%, and the chroma is 57.
Example 2A method for preparing a methacryloyloxyethyl dimethylbenzyl ammonium chloride solution comprises the following steps:
ensuring that a reaction kettle is clean and anhydrous, adding 33.5wt% of dimethylaminoethyl methacrylate and 50ppm of chelating agent into the reaction kettle according to the mass fraction, starting stirring and heating, heating to 45 ℃, starting dropwise adding 9.5wt% of benzyl chloride, adding 5.0wt% of deionized water after dropwise adding, and reacting for 18min; continuously dropwise adding 8.5wt% of benzyl chloride, reacting for 25min after dropwise adding, and then adding 9.0wt% of deionized water; continuously dropwise adding 8.0wt% of benzyl chloride, and finishing the heat preservation reaction for 150min; the temperature of the whole reaction process is controlled to be 45-55 ℃; and after the heat preservation is finished, adding 26.5wt% of deionized water and 1000ppm of polymerization inhibitor, stirring uniformly, and degassing in vacuum (-0.02-0.09KMP, 45 ℃) for 120min to obtain the methacryloyloxyethyl dimethyl benzyl ammonium chloride solution.
The detection method was the same as in example 1. Through detection, the content of the obtained methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 60.5%, the pH value is 6.74, the acid value is 0.010%, and the chroma is 60.
Example 3A method for preparing a methacryloyloxyethyl dimethylbenzyl ammonium chloride solution comprises the following steps:
ensuring that a reaction kettle is clean and anhydrous, adding 34.0wt% of dimethylaminoethyl methacrylate and 40ppm of chelating agent into the reaction kettle according to the mass fraction, starting stirring and heating, heating to 43 ℃, starting dropwise adding 7.5wt% of benzyl chloride, adding 6.0wt% of deionized water after dropwise adding, and reacting for 20min; continuously dropwise adding 9.0wt% of benzyl chloride, reacting for 20min after dropwise adding, and then adding 7.5wt% of deionized water; continuously dropwise adding 8.5wt% of benzyl chloride, and keeping the temperature for reaction for 160min after the dropwise adding is finished; the temperature of the whole reaction process is controlled at 43-55 ℃; and after the heat preservation is finished, continuously adding 27.5wt% of deionized water and 800ppm of polymerization inhibitor, uniformly stirring, and vacuum degassing (-0.02-0.09KMP, 45 ℃) for 100min to obtain the methacryloyloxyethyl dimethyl benzyl ammonium chloride solution.
The detection method was the same as in example 1. Through detection, the content of the obtained methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 59.7%, the pH value is 6.07, the acid value is 0.096%, and the chroma is 61.
Example 4A preparation method of a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution comprises the following steps:
ensuring that a reaction kettle is clean and anhydrous, adding 35wt% of dimethylaminoethyl methacrylate and 30ppm of chelating agent into the reaction kettle according to the mass fraction, starting stirring and heating, heating to 50 ℃, starting dropwise adding 9.1wt% of benzyl chloride, adding 5.0wt% of deionized water after dropwise adding, and reacting for 17min; continuously dropwise adding 10.7wt% of benzyl chloride, finishing the reaction for 28min after dropwise adding, and then adding 8.5wt% of deionized water; continuously dropwise adding 8.3wt% of benzyl chloride, and after finishing dropwise adding, keeping the temperature and reacting for 80min; the temperature is controlled between 45 and 55 ℃ in the whole reaction process; and after the heat preservation is finished, adding 23.4wt% of deionized water and 700ppm of polymerization inhibitor, stirring uniformly, and degassing in vacuum (-0.02-0.09KMP, 50 ℃) for 110min to obtain the methacryloyloxyethyl dimethyl benzyl ammonium chloride solution.
The detection method was the same as in example 1. Through detection, the content of the obtained methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 60.8%, the pH value is 6.71, the acid value is 0.012%, and the chroma is 50.
Example 5A method for preparing a methacryloyloxyethyl dimethylbenzyl ammonium chloride solution comprises the following steps:
ensuring that a reaction kettle is clean and anhydrous, adding 30.5wt% of dimethylaminoethyl methacrylate and 20ppm of chelating agent into the reaction kettle according to the mass fraction, starting stirring and heating, heating to 40 ℃, starting dropwise adding 7.9wt% of benzyl chloride, adding 4.7wt% of deionized water after dropwise adding, and reacting for 13min; continuously dropwise adding 9.5wt% of benzyl chloride, reacting for 25min after dropwise adding, and then adding 10.0wt% of deionized water; continuously dropwise adding 7.5wt% of benzyl chloride, and finishing the heat preservation reaction for 170min; the temperature is controlled to be 40-55 ℃ in the whole reaction process; and after the heat preservation is finished, continuously adding 29.9wt% of deionized water and 600ppm of polymerization inhibitor, uniformly stirring, and vacuum degassing (-0.02-0.09KMP, 50 ℃) for 100min to obtain the methacryloyloxyethyl dimethyl benzyl ammonium chloride solution.
The detection method was the same as in example 1. Through detection, the content of the obtained methacryloyloxyethyl dimethyl benzyl ammonium chloride solution is 59.0%, the pH value is 6.94, the acid value is 0.071%, and the chroma is 48.
Comparative example 1A preparation method of a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution comprises the following steps:
ensuring that the reaction kettle is clean, adding 42wt% of deionized water, 32.5wt% of dimethylaminoethyl methacrylate and 10ppm of chelating agent into the reaction kettle according to mass fraction, and starting stirring and heating. Heating to 40 ℃, and beginning to dropwise add 25.5% benzyl chloride for 120min, wherein the temperature is controlled to be 35-45 ℃ in the dropwise adding process. And (4) after the dropwise addition is finished, continuously preserving the heat for 60min, adding 500ppm of polymerization inhibitor after the heat preservation is finished, and uniformly stirring to obtain a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution.
The detection method was the same as in example 1. Through detection, the content of the obtained methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 60.1%, the pH value is 4.82, the acid value is 2.721%, and the chroma is 79.
Comparative example 2A method for preparing a methacryloyloxyethyl dimethylbenzyl ammonium chloride solution comprises the following steps:
the same as example 1 except that the vacuum degassing 90min step was omitted.
The final methacryloyloxyethyl dimethylbenzyl ammonium chloride solution had a content of 60.1%, a pH of 6.18, an acid value of 1.054% and a color of 57.
Test example 1
The product obtained in example 1 is placed still for 6 months, the acid value is changed from 0.086% to 0.076%, the reduction range is small, and the product obtained in the application has strong stability.
The acid value of the products obtained in the comparative examples 1 and 2 is changed from 2.721% to 5.122% and from 1.054% to 1.873% after the products obtained in the comparative examples 1 and 2 are respectively placed still for 1 month, so that the products obtained in the comparative examples 1 and 2 are not only high in acid value but also poor in stability.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is characterized by comprising the following steps:
adding 30-35 parts by weight of dimethylaminoethyl methacrylate into a reaction kettle, then adding a chelating agent, stirring, and heating to 35-55 ℃;
dripping 7.0-10.0 weight parts of benzyl chloride once, then adding 3.0-5.0 weight parts of deionized water, and reacting for 10-20 min;
8.5 to 12.0 weight parts of benzyl chloride is dripped for the second time to react for 15 to 30min, and then 8.0 to 10.0 weight parts of deionized water is added;
dropwise adding 6.5-9.0 parts by weight of benzyl chloride for three times, reacting for 60-180 min, adding 23-30 parts by weight of deionized water, adding a polymerization inhibitor, stirring, and vacuum degassing for 60-120 min to obtain a methacryloyloxyethyl dimethyl benzyl ammonium chloride solution;
wherein the sum of the parts by weight of the dimethylaminoethyl methacrylate, the benzyl chloride and the deionized water is 100.
2. The method according to claim 1,
the chelating agent comprises at least one of disodium ethylene diamine tetracaproate and tetrasodium ethylene diamine tetracaproate.
3. The method according to claim 1,
the content of the chelating agent in the methacryloyloxyethyl dimethylbenzyl ammonium chloride solution is 10-50 ppm.
4. The production method according to claim 1,
the polymerization inhibitor is p-hydroxyanisole.
5. The production method according to claim 1,
the content of the polymerization inhibitor in the methacryloyloxyethyl dimethyl benzyl ammonium chloride solution is 500-1000 ppm.
6. The production method according to claim 1,
the pressure of vacuum degassing is-0.02 to-0.09 KMP, and the temperature of vacuum degassing is 40 to 55 ℃.
7. The production method according to claim 1,
the reaction temperature in the whole process is controlled to be 35-55 ℃.
8. The method according to claim 1,
the reaction kettle is an anhydrous reaction kettle in the kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211317771.4A CN115745813A (en) | 2022-10-26 | 2022-10-26 | Preparation method of methacryloyloxyethyl dimethyl benzyl ammonium chloride solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211317771.4A CN115745813A (en) | 2022-10-26 | 2022-10-26 | Preparation method of methacryloyloxyethyl dimethyl benzyl ammonium chloride solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115745813A true CN115745813A (en) | 2023-03-07 |
Family
ID=85353372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211317771.4A Pending CN115745813A (en) | 2022-10-26 | 2022-10-26 | Preparation method of methacryloyloxyethyl dimethyl benzyl ammonium chloride solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115745813A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4745214A (en) * | 1986-06-20 | 1988-05-17 | Norsolor | Process for the preparation of an aqueous solution of unsaturated quaternary ammonium salts |
| JPH02212457A (en) * | 1989-02-14 | 1990-08-23 | Mitsubishi Gas Chem Co Inc | Production of unsaturated quaternary ammonium salt |
| JPH03135945A (en) * | 1989-07-07 | 1991-06-10 | Nippon Shokubai Kagaku Kogyo Co Ltd | Quaternary ammonium salt and production thereof |
| JPH07267906A (en) * | 1994-03-30 | 1995-10-17 | Kohjin Co Ltd | Production of aqueous solution of unsaturated quaternary ammonium salt |
| CN1174188A (en) * | 1996-07-08 | 1998-02-25 | 埃勒夫阿托化学有限公司 | Stabilized aqueous solutions of unsaturated quaternary ammonium salts |
| CN1176961A (en) * | 1996-07-08 | 1998-03-25 | 埃勒夫阿托化学有限公司 | Process for manufacture of aqueous solutions of unsaturated quaternary ammonium salts |
| CN1337935A (en) * | 1999-01-21 | 2002-02-27 | 埃勒夫阿托化学有限公司 | Method for making aqueous solutions of unsaturated quaternary ammonium salts |
| CN1337936A (en) * | 1999-01-21 | 2002-02-27 | 埃勒夫阿托化学有限公司 | Method for making aqueous solutions of unsaturated quaternary ammonium salts |
| CN1384095A (en) * | 2001-04-27 | 2002-12-11 | 阿托菲纳公司 | Prepn of water solution of unsaturated quaternary ammonium salt |
| US20040024242A1 (en) * | 2000-08-11 | 2004-02-05 | Alain Riondel | Method for making aqueous solutions of (meth)acryloyloxyethylbenzyldimethylammonium chlorides |
| CN101050182A (en) * | 2006-04-06 | 2007-10-10 | 浙江华特实业集团华特化工有限公司 | Method for preparing quaternary ammonium salt |
-
2022
- 2022-10-26 CN CN202211317771.4A patent/CN115745813A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4745214A (en) * | 1986-06-20 | 1988-05-17 | Norsolor | Process for the preparation of an aqueous solution of unsaturated quaternary ammonium salts |
| JPH02212457A (en) * | 1989-02-14 | 1990-08-23 | Mitsubishi Gas Chem Co Inc | Production of unsaturated quaternary ammonium salt |
| JPH03135945A (en) * | 1989-07-07 | 1991-06-10 | Nippon Shokubai Kagaku Kogyo Co Ltd | Quaternary ammonium salt and production thereof |
| JPH07267906A (en) * | 1994-03-30 | 1995-10-17 | Kohjin Co Ltd | Production of aqueous solution of unsaturated quaternary ammonium salt |
| CN1174188A (en) * | 1996-07-08 | 1998-02-25 | 埃勒夫阿托化学有限公司 | Stabilized aqueous solutions of unsaturated quaternary ammonium salts |
| CN1176961A (en) * | 1996-07-08 | 1998-03-25 | 埃勒夫阿托化学有限公司 | Process for manufacture of aqueous solutions of unsaturated quaternary ammonium salts |
| CN1337935A (en) * | 1999-01-21 | 2002-02-27 | 埃勒夫阿托化学有限公司 | Method for making aqueous solutions of unsaturated quaternary ammonium salts |
| CN1337936A (en) * | 1999-01-21 | 2002-02-27 | 埃勒夫阿托化学有限公司 | Method for making aqueous solutions of unsaturated quaternary ammonium salts |
| US20040024242A1 (en) * | 2000-08-11 | 2004-02-05 | Alain Riondel | Method for making aqueous solutions of (meth)acryloyloxyethylbenzyldimethylammonium chlorides |
| CN1384095A (en) * | 2001-04-27 | 2002-12-11 | 阿托菲纳公司 | Prepn of water solution of unsaturated quaternary ammonium salt |
| CN101050182A (en) * | 2006-04-06 | 2007-10-10 | 浙江华特实业集团华特化工有限公司 | Method for preparing quaternary ammonium salt |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0396303B1 (en) | Process for producing and use of maleic acid (co-) polymer salt improved in biodegradability | |
| US4709091A (en) | Production of polymaleic acid | |
| US3933766A (en) | Manufacture of insoluble and only sparingly swellable poly-N-vinylpyrrolidone-2 or copolymers of N-vinylpyrrolidone with other N-vinyllactams | |
| CN115745813A (en) | Preparation method of methacryloyloxyethyl dimethyl benzyl ammonium chloride solution | |
| US4455411A (en) | Process for preparing acrylamide polymers | |
| US20090223645A1 (en) | Method and composition for improved temporary wet strength | |
| DE4221863C2 (en) | Copolymers of allyliminodiacetic acid with unsaturated carboxylic acids and their use as complexing agents, peroxide stabilizers, builders in detergents and cleaners and dispersants | |
| CN111285966B (en) | Modified strong anionic polymer flocculant and preparation method thereof | |
| DE2446257A1 (en) | PROCESS FOR THE PRODUCTION OF WATER-SOLUBLE HIGH MOLECULAR POLYACRYLAMIDE | |
| CN112225843A (en) | Ternary scale inhibitor and preparation method thereof | |
| US4816508A (en) | Stabilized cationic acrylate or methacrylate polymer admixtures | |
| CN106317306B (en) | A kind of preparation method of cationic polyacrylamide | |
| CN114262406A (en) | Emulsion thickener and preparation method thereof | |
| JP5076864B2 (en) | Acrylic acid (salt) / maleic acid (salt) copolymer aqueous solution and method for producing the same | |
| US5214089A (en) | Stabilized aqueous solution of a C1 -C5 alkyl vinyl ether and maleic acid copolymer | |
| US4086146A (en) | Water treating process | |
| CN112608426A (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| US3333925A (en) | Stannate type stabilizer compositions and preparation thereof | |
| JPH05287690A (en) | Scale sticking prevention in digester in kraft pulp production process | |
| CN112552439B (en) | Cationic polymer and preparation method thereof | |
| CN110066027B (en) | Phosphorus-free corrosion and scale inhibitor composition, phosphorus-free corrosion and scale inhibitor and application thereof | |
| CN116462802B (en) | Environment-friendly scale inhibition dispersing agent and preparation method thereof | |
| CN1288182C (en) | Process for preparing still release agent | |
| CN118126236A (en) | Net-shaped anti-degradation cationic polyacrylamide and preparation method thereof | |
| JPH0860593A (en) | Paper strengthening agent and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230307 |