CN114292214A - Alkylphenol ethoxylated ammonium sulfate salt for emulsion polymerization and preparation method thereof - Google Patents
Alkylphenol ethoxylated ammonium sulfate salt for emulsion polymerization and preparation method thereof Download PDFInfo
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000010556 emulsion polymerization method Methods 0.000 title description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 25
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 22
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- 239000006172 buffering agent Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000013543 active substance Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 11
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 10
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 claims description 10
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000001630 malic acid Substances 0.000 claims description 10
- 235000011090 malic acid Nutrition 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- TUMNHQRORINJKE-UHFFFAOYSA-N 1,1-diethylurea Chemical compound CCN(CC)C(N)=O TUMNHQRORINJKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- MOCKWYUCPREFCZ-UHFFFAOYSA-N chondroitin sulfate E (GalNAc4,6diS-GlcA), precursor 5a Chemical compound NNC(=O)NC1=CC=CC=C1 MOCKWYUCPREFCZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000007046 ethoxylation reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 9
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 9
- 239000000203 mixture Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000006386 neutralization reaction Methods 0.000 description 16
- 238000005070 sampling Methods 0.000 description 16
- -1 ammonium alkyl phenol ethoxylated sulfate salt Chemical class 0.000 description 10
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000005486 sulfidation Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- XMRUJYGYYCLRGJ-UHFFFAOYSA-N azanium;2-[2-[2-[2-(4-nonylphenoxy)ethoxy]ethoxy]ethoxy]ethyl sulfate Chemical compound [NH4+].CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOS([O-])(=O)=O)C=C1 XMRUJYGYYCLRGJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of alkylphenol ethoxylate ammonium sulfate for emulsion polymerization. The alkylphenol ethoxylate ammonium sulfate with low chroma is prepared by optimizing the production process and adding a buffering agent. Simultaneously, the volatile content of the product is reduced by adding a non-ionic diluent, and the mass ratio of the alkylphenol ethoxylate to the non-ionic diluent is specifically 100: the optimal level is reached at 28.8. So that the alkylphenol ethoxylate ammonium sulfate salt is convenient and quick to produce and use and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and a preparation method thereof.
Background
The alkylphenol ethoxylate ammonium sulfate serving as a derivative of the alkylphenol ethoxylate has both nonionic activity and anionic activity due to ethoxy and sulfuric acid groups in molecules, and the product has the excellent characteristics of the alkylphenol ethoxylate, and also has the advantages of strong foamability, detergency, permeability, emulsibility, excellent hard water resistance, good calcium soap dispersion phase, remarkable solubilizing capability and small irritation to a human body. Therefore, the product becomes an important auxiliary agent for cosmetics and various household and industrial products.
At present, the method for preparing the alkylphenol ethoxylate ammonium sulfate is to carry out a sulfurization reaction by adopting sulfamic acid and alkylphenol ethoxylate. However, the current products contain 13-16% of ethanol, and when the products are used for producing the water-based polymer, the ethanol solution volatilizes, a large amount of volatile components are generated, and the environment is influenced. And the color is high, the paint is pasty at normal temperature, the production of the water-based polymer is not facilitated, and the produced polymer paint film is easy to yellow.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above problems occurring in the prior art.
Accordingly, it is an object of the present invention to provide an ammonium alkyl phenol ethoxylated sulfate salt for emulsion polymerization and a method for preparing the same.
To solve the above technical problem, according to an aspect of the present invention, the present invention provides the following technical solutions: an alkyl phenol ethoxylation ammonium sulfate salt for emulsion polymerization and a preparation method thereof, which comprises the following steps,
dehydrating the alkylphenol ethoxylate; and mixing the dehydrated alkylphenol ethoxylate, a vulcanizing agent and a vulcanization catalyst for reaction to obtain a colorless product, adding a non-ionic diluent, a buffering agent and deionized water for mixing and adjusting the pH, and obtaining alkylphenol ethoxylate ammonium sulfate after the vulcanization reaction is finished.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: the chemical formula of the alkylphenol ethoxylate is shown as follows; wherein R represents the number of carbon atoms and is 5-20; and n is the degree of polymerization.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: and the dehydration step comprises introducing inert gas into the alkylphenol ethoxylate for replacement, and heating to 40-60 ℃ until the moisture content is less than 5%.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: the vulcanizing agents include, but are not limited to, sulfamic acid; the sulfurization catalyst is one or more of alkyl or phenyl substituted urea compounds, including but not limited to one or more of N, N-dimethyl urea, N, N-diethyl urea and 4-phenyl semicarbazide.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: the mixing reaction further comprises the step of mixing the raw materials,
firstly, adding the dehydrated alkylphenol ethoxylate and a vulcanization catalyst into a reaction kettle, stirring for 20min, then slowly adding a vulcanizing agent, heating to 110-130 ℃, and reacting for 3-5 h.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: the molar ratio of the alkylphenol ethoxylate to the vulcanizing agent to the vulcanizing catalyst is 1: 1-1.2: 0.01 to 0.1.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: the non-ionic diluent comprises one or two of polyethylene glycol and polypropylene glycol with the molecular weight of 100-800, and the addition amount is 15-20% of the total mass.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: the buffer comprises one or more of phosphoric acid, citric acid and malic acid, and the addition amount is 0.01-0.05% of the total mass; the addition amount of the deionized water is 15-20% of the total mass, so that the solid content is 60-62%.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: the pH value is adjusted to 9-10 by NaOH or KOH.
As a preferable scheme of the alkylphenol ethoxylate ammonium sulfate for emulsion polymerization and the preparation method thereof, the method comprises the following steps: and (3) finishing the vulcanization reaction, wherein the content of the alkylphenol ethoxylate ammonium sulfate anion active substance in the final product is 58-60%.
The invention has the beneficial effects that:
the invention provides a preparation method of alkylphenol ethoxylate ammonium sulfate for emulsion polymerization. The alkylphenol ethoxylate ammonium sulfate with low chroma is prepared by optimizing the production process and adding a buffering agent. Simultaneously, the volatile content of the product is reduced by adding a non-ionic diluent, and the mass ratio of the nonyl phenol ethoxylate to the non-ionic diluent is specifically 100: the optimal level is reached at 28.8. So that the alkylphenol ethoxylate ammonium sulfate salt is convenient and quick to produce and use and is environment-friendly.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The content, the chromaticity and the viscosity of the anion active substances detected in the embodiment of the invention are measured according to the following methods:
anion active content determination standard: GB/T5173 and 2018, namely a direct two-phase titration method for determining the contents of a surfactant, a detergent and an anionic active substance;
and (3) colorimetric determination standard: GB/T3143-1982 liquid chemical product color determination method;
and (3) viscosity measurement standard: measuring the viscosity of the liquid in GB/T22235-;
the reagents used in the examples of the present invention are generally commercially available unless otherwise specified.
Example 1:
100g of nonylphenol ethoxy compound (n is 4) is added into a normal pressure reaction kettle, nitrogen is introduced into the reaction kettle, the temperature is raised to 60 ℃, and sampling is carried out to analyze moisture, wherein the moisture requirement is less than 0.2 percent, and the oxygen content is less than 0.2 percent.
After the water content was qualified, 2.2g of sulfidation catalyst N, N-dimethylurea was added and stirred for 10 minutes. Then, 29.2g of sulfamic acid was slowly added thereto, and stirred for 10 minutes. The temperature of the reaction kettle is raised to 130 ℃, the reaction is carried out for 1 hour, and the content of the anion active matter is detected to reach more than 94 percent by sampling.
38g of pure water, 20030 g of nonionic diluent PEG-20030 g, 2g of malic acid and 10g of sodium hydroxide are added into a neutralization kettle and stirred for 20 minutes. The sample was analyzed for pH 10. And transferring the materials in the reaction kettle to a neutralization kettle after the content of the anion active substances in the reaction kettle is more than 90 percent. Stirred for 20 minutes and sampled for analysis of colour 10, viscosity 100mpa, s, pH 8.5, active content: 60.5 percent.
Example 2:
100g of nonylphenol ethoxy compound (n is 10) is added into a normal pressure reaction kettle, nitrogen is introduced into the reaction kettle, the temperature is raised to 60 ℃, and sampling is carried out to analyze moisture, wherein the moisture requirement is less than 1 percent, and the oxygen content is less than 0.2 percent.
After the water content was qualified, 2.28g of sulfidation catalyst N, N-dimethylurea was added and stirred for 10 minutes. Then, 16.9g of sulfamic acid was slowly added thereto, and stirred for 10 minutes. The temperature of the reaction kettle is raised to 130 ℃, the reaction is carried out for 1 hour, and the content of the anion active matter is detected to reach more than 94 percent by sampling.
38g of pure water, PPG-20028.8 g of nonionic diluent, 2g of malic acid and 15g of sodium hydroxide are added into a neutralization kettle and stirred for 20 minutes. The sample was analyzed for pH 10. And transferring the materials in the reaction kettle to a neutralization kettle after the content of the anion active substances in the reaction kettle is more than 90 percent. Stirring for 20 minutes a sample was taken which analyzed colour number 100, viscosity 151mpa, s, pH 7.65, active content: and (5) 59.8%.
Example 3:
100g of nonylphenol ethoxy compound (n is 10) is added into a normal pressure reaction kettle, nitrogen is introduced into the reaction kettle, the temperature is raised to 60 ℃, and sampling is carried out to analyze moisture, wherein the moisture requirement is less than 0.5 percent, and the oxygen content is less than 0.2 percent.
After the water content was qualified, 2.28g of sulfidation catalyst N, N-dimethylurea was added and stirred for 10 minutes. Then, 16.9g of sulfamic acid was slowly added thereto, and stirred for 10 minutes. And (3) heating the reaction kettle to 130 ℃, reacting for 1 hour, and sampling to detect the content of the anion active substances.
38g of pure water, PPG-20028.8 g of nonionic diluent, 2g of malic acid and 15g of sodium hydroxide are added into a neutralization kettle and stirred for 20 minutes. The sample was analyzed for pH 10. And transferring the materials in the reaction kettle to a neutralization kettle after the content of the anion active substances in the reaction kettle is more than 90 percent. Sample analysis color 45, viscosity 151mpa, s, pH 7.65, actives content with stirring 20 min: 60.2 percent.
Example 4:
100g of nonylphenol ethoxy compound (n is 10) is added into a normal pressure reaction kettle, nitrogen is introduced into the reaction kettle, the temperature is raised to 60 ℃, and sampling is carried out to analyze moisture, wherein the moisture requirement is less than 0.2 percent, and the oxygen content is less than 0.2 percent.
After the water content was qualified, 2.28g of sulfidation catalyst N, N-dimethylurea was added and stirred for 10 minutes. Then, 16.9g of sulfamic acid was slowly added thereto, and stirred for 10 minutes. And (3) heating the reaction kettle to 130 ℃, reacting for 1 hour, and sampling to detect the content of the anion active substances.
38g of pure water, PPG-20028.8 g of nonionic diluent, 2g of malic acid and 15g of sodium hydroxide are added into a neutralization kettle and stirred for 20 minutes. The sample was analyzed for pH 10. And transferring the materials in the reaction kettle to a neutralization kettle after the content of the anion active substances in the reaction kettle is more than 90 percent. Stirring for 20 minutes a sample was taken which analyzed colour 10, viscosity 151mpa, s, pH 7.65, active content: and (5) 59.9%.
Example 5:
100g of nonylphenol ethoxy compound (n is 4) is added into a normal pressure reaction kettle, nitrogen is introduced into the reaction kettle, the temperature is raised to 60 ℃, and sampling is carried out to analyze moisture, wherein the moisture requirement is less than 0.2 percent, and the oxygen content is less than 0.2 percent.
After the water content was qualified, 2.2g of sulfidation catalyst N, N-dimethylurea was added and stirred for 10 minutes. Then, 29.2g of sulfamic acid was slowly added thereto, and stirred for 10 minutes. And (3) heating the reaction kettle to 130 ℃, reacting for 1 hour, and sampling to detect the content of the anion active substances.
38g of pure water, 2g of nonionic diluent PEG-20028.8 g, 2g of malic acid and 10g of sodium hydroxide are added into a neutralization kettle and stirred for 20 minutes. The sample was analyzed for pH 10. And transferring the materials in the reaction kettle to a neutralization kettle after the content of the anion active substances in the reaction kettle is more than 90 percent. Stirred for 20 minutes and sampled for analysis of colour 10, viscosity 100mpa, s, pH 8.5, active content: 60.2 percent.
Example 6:
100g of nonylphenol ethoxy compound (n is 4) is added into a normal pressure reaction kettle, nitrogen is introduced into the reaction kettle, the temperature is raised to 60 ℃, and sampling is carried out to analyze moisture, wherein the moisture requirement is less than 0.2 percent, and the oxygen content is less than 0.2 percent.
After the water content was qualified, 2.2g of sulfidation catalyst N, N-dimethylurea was added and stirred for 10 minutes. Then, 29.2g of sulfamic acid was slowly added thereto, and stirred for 10 minutes. And (3) heating the reaction kettle to 130 ℃, reacting for 1 hour, and sampling to detect the content of the anion active substances.
38g of pure water, 20020 g of nonionic diluent PEG-20020 g, 2g of malic acid and 10g of sodium hydroxide are added into a neutralization kettle and stirred for 20 minutes. The sample was analyzed for pH 10. And transferring the materials in the reaction kettle to a neutralization kettle after the content of the anion active substances in the reaction kettle is more than 90 percent. Stirred for 20 minutes and sampled for analysis of colour 10, viscosity 100mpa, s, pH 8.5, active content: 60.5 percent.
Example 7:
100g of nonylphenol ethoxy compound (n is 4) is added into a normal pressure reaction kettle, nitrogen is introduced into the reaction kettle, the temperature is raised to 60 ℃, and sampling is carried out to analyze moisture, wherein the moisture requirement is less than 0.2 percent, and the oxygen content is less than 0.2 percent.
After the water content was qualified, 2.2g of sulfidation catalyst N, N-dimethylurea was added and stirred for 10 minutes. Then, 29.2g of sulfamic acid was slowly added thereto, and stirred for 10 minutes. And (3) heating the reaction kettle to 130 ℃, reacting for 1 hour, and sampling to detect the content of the anion active substances.
38g of pure water, 20040 g of nonionic diluent PEG-20040 g, 2g of malic acid and 10g of sodium hydroxide are added into a neutralization kettle and stirred for 20 minutes. The sample was analyzed for pH 10. And transferring the materials in the reaction kettle to a neutralization kettle after the content of the anion active substances in the reaction kettle is more than 90 percent. Stirred for 20 minutes and sampled for analysis of colour 10, viscosity 100mpa, s, pH 8.5, active content: 52.2 percent.
Example 7:
100g of nonylphenol ethoxy compound (n is 4) is added into a normal pressure reaction kettle, nitrogen is introduced into the reaction kettle, the temperature is raised to 60 ℃, and sampling is carried out to analyze moisture, wherein the moisture requirement is less than 0.2 percent, and the oxygen content is less than 0.2 percent.
After the water content was qualified, 2.2g of sulfidation catalyst N, N-dimethylurea was added and stirred for 10 minutes. Then, 29.2g of sulfamic acid was slowly added thereto, and stirred for 10 minutes. And (3) heating the reaction kettle to 130 ℃, reacting for 1 hour, and sampling to detect the content of the anion active substances.
38g of pure water, 20040 g of nonionic diluent PEG-20040 g, 2g of malic acid and 10g of sodium hydroxide are added into a neutralization kettle and stirred for 20 minutes. The sample was analyzed for pH 10. And transferring the materials in the reaction kettle to a neutralization kettle after the content of the anion active substances in the reaction kettle is more than 90 percent. Stirred for 20 minutes and sampled for analysis of colour 10, viscosity 100mpa, s, pH 8.5, active content: 52.2 percent.
Example 8:
volatile content measurements were performed on examples 1 to 7 and on commercially available samples, respectively, and the measurement procedure was as follows:
test methods gas chromatography was performed according to ISO 11890-2 determination of Volatile Organic Compound (VOC) content in paints and varnishes. Sample 1 was purchased from Shanghai loyal Fine chemical, CO-436, and sample 2 was purchased from Solvay, CO-436.
The comparative data obtained are as follows:
TABLE 1
The addition of the non-ionic diluent can reduce the viscosity of the product because the alkylphenol ethoxylates are compatible with the non-ionic diluent, and because the boiling point of the non-ionic diluent exceeds 260 ℃, only a small amount of volatile organic compounds are generated during the detection of VOCs. However, when the addition amount of the nonionic diluent exceeds 20% of the total mass, the product performance is adversely affected, and when the addition amount of the nonionic emulsifier exceeds 20% of the total mass, the active content of the final product is lower than 58%, and the downstream application of the product is affected.
Example 9:
the starting alkylphenol ethoxylate was replaced by the same procedure as in example 1. And detecting the obtained product. The details are shown in Table 2.
TABLE 2
The invention provides a preparation method of alkylphenol ethoxylate ammonium sulfate for emulsion polymerization. The alkylphenol ethoxylate ammonium sulfate with low chroma is prepared by optimizing the production process and adding a buffering agent. Simultaneously, the volatile content of the product is reduced by adding a non-ionic diluent, and the mass ratio of the alkylphenol ethoxylate to the non-ionic diluent is specifically 100: the optimal level is reached at 28.8. So that the alkylphenol ethoxylate ammonium sulfate salt is convenient and quick to produce and use and is environment-friendly.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. An alkylphenol ethoxylation ammonium sulfate salt for emulsion polymerization and a preparation method thereof are characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
dehydrating the alkylphenol ethoxylate; and mixing the dehydrated alkylphenol ethoxylate, a vulcanizing agent and a vulcanization catalyst for reaction to obtain a colorless product, adding a non-ionic diluent, a buffering agent and deionized water for mixing and adjusting the pH, and obtaining alkylphenol ethoxylate ammonium sulfate after the vulcanization reaction is finished.
2. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: the chemical formula of the alkylphenol ethoxylate is shown as follows; wherein R represents the number of carbon atoms and is 5-20; and n is the degree of polymerization.
3. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: and the dehydration step comprises introducing inert gas into the alkylphenol ethoxylate for replacement, and heating to 40-60 ℃ until the moisture content is less than 5%.
4. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: the vulcanizing agents include, but are not limited to, sulfamic acid; the sulfurization catalyst is one or more of alkyl or phenyl substituted urea compounds, including but not limited to one or more of N, N-dimethyl urea, N, N-diethyl urea and 4-phenyl semicarbazide.
5. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: the mixing reaction further comprises the step of mixing the raw materials,
firstly, adding the dehydrated alkylphenol ethoxylate and a vulcanization catalyst into a reaction kettle, stirring for 20min, then slowly adding a vulcanizing agent, heating to 110-130 ℃, and reacting for 3-5 h.
6. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: the molar ratio of the alkylphenol ethoxylate to the vulcanizing agent to the vulcanizing catalyst is 1: 1-1.2: 0.01 to 0.1.
7. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: the non-ionic diluent comprises one or two of polyethylene glycol and polypropylene glycol with the molecular weight of 100-800, and the addition amount is 15-20% of the total mass.
8. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: the buffer comprises one or more of phosphoric acid, citric acid and malic acid, and the addition amount is 0.01-0.05% of the total mass; the addition amount of the deionized water is 15-20% of the total mass, so that the solid content of the final product, namely the alkylphenol ethoxylate ammonium sulfate salt is 60-62%.
9. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: the pH value is adjusted to 9-10 by NaOH or KOH.
10. The ammonium alkyl phenol ethoxylate sulfate salt for emulsion polymerization according to claim 1 and the method for preparing the same, wherein: and (3) finishing the vulcanization reaction, wherein the content of the alkylphenol ethoxylate ammonium sulfate anion active substance in the final product is 58-60%.
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