CN117003933A - Soap-free polymeric cationic dispersion and preparation method thereof - Google Patents
Soap-free polymeric cationic dispersion and preparation method thereof Download PDFInfo
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- CN117003933A CN117003933A CN202311016183.1A CN202311016183A CN117003933A CN 117003933 A CN117003933 A CN 117003933A CN 202311016183 A CN202311016183 A CN 202311016183A CN 117003933 A CN117003933 A CN 117003933A
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- soap
- acrylate
- cationic dispersion
- acrylic ester
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- 239000006185 dispersion Substances 0.000 title claims abstract description 46
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- -1 acrylic ester Chemical class 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 34
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 28
- 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 25
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 238000010438 heat treatment Methods 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 20
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 11
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 4
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000011534 incubation Methods 0.000 claims 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 1
- 239000001263 FEMA 3042 Substances 0.000 abstract description 11
- 229940033123 tannic acid Drugs 0.000 abstract description 11
- 229920002258 tannic acid Polymers 0.000 abstract description 11
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 abstract description 9
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 abstract description 9
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 abstract description 9
- 235000015523 tannic acid Nutrition 0.000 abstract description 9
- 150000001768 cations Chemical class 0.000 abstract description 8
- 230000002265 prevention Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 36
- 239000008367 deionised water Substances 0.000 description 36
- 229910021641 deionized water Inorganic materials 0.000 description 36
- 239000011259 mixed solution Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 27
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 230000037452 priming Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a soap-free polymerized cationic dispersion and a preparation method thereof, wherein the soap-free polymerized cationic dispersion is prepared from the following components in parts by mass: 500-1000 parts of emulsifying agent, 10-20 parts of initial introduction, 100-500 parts of polymerized monomer, 0.5-10 parts of silane coupling agent, 0.5-5 parts of initiator, 0.5-5 parts of oxidant, 0.5-5 parts of reducing agent and water; wherein the emulsifier is obtained by reacting DMAEMA, an acrylic ester monomer, a styrene monomer and modified acrylic ester; the modified acrylic ester is obtained by reacting triglycidyl isocyanurate with acrylic acid. The dispersion can be used in outer wall covers or woodware primer, has the unique characteristic of cations due to the introduction of DMAEMA, realizes the performances of high stain resistance, high water resistance, dust prevention and tannic acid prevention, and overcomes the defects existing in the existing products.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a soap-free polymerized cationic dispersion and a preparation method thereof.
Background
Wooden furniture is an indispensable article in life, and the surface of the wooden furniture is usually coated with water-based wood paint, so that the paint has the advantages of environmental protection, health, attractive appearance and good protection, and is well accepted and favored by consumers.
However, for the substrate containing tannic acid, the common water paint coating has the problems of possible color change, poor grease sealing effect and the like. With the temperature change and time accumulation, substances such as tannic acid in the wood gradually exude, migrate into the coating film, and cause phenomena such as discoloration, swelling, falling, adhesion drop and the like of the coating film, thereby seriously affecting the coating effect and the service life of furniture. Therefore, the existing woodenware primer has more defects, and the requirements of consumers are difficult to meet.
In view of the foregoing, there is a need to develop a new technical solution to solve the problems in the prior art.
Disclosure of Invention
Based on this, the invention discloses a soap-free polymeric cationic dispersion and a method of preparing the same. The invention adopts DMAEMA (N, N-dimethylaminoethyl methacrylate), acrylate monomer, styrene monomer and modified acrylate as raw materials to prepare an emulsifier, and then uses the emulsifier as a kettle bottom to perform emulsion polymerization on a polymerized monomer to obtain a dispersoid. The dispersion can be used in an outer wall cover or woodware primer, has the unique characteristic of cations due to the introduction of DMAEMA, realizes the performances of high stain resistance, high water resistance, dust prevention and tannic acid prevention, and overcomes the defects existing in the existing products.
The invention aims at providing a soap-free polymerized cationic dispersion, which is prepared from the following components in parts by weight:
wherein,
the emulsifier is obtained by reacting DMAEMA, an acrylic ester monomer, a styrene monomer and modified acrylic ester;
the modified acrylic ester is obtained by reacting triglycidyl isocyanurate with acrylic acid.
Further, the acrylic ester monomer is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate.
Further, the polymeric monomer is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.
Further, the polymerization monomers are Methyl Methacrylate (MMA), butyl Acrylate (BA), 2-ethylhexyl acrylate (2-EHA), trimethylolpropane trimethacrylate (SR-350) and 2-hydroxyethyl acrylate (HEA).
Further, the initial introduction is an initiator solution with a concentration of 1-10%.
Further, the oxidizing agent is tert-butyl peroxide (TBHP).
Further, the reducing agent is FF6M.
Further, the silane coupling agent is vinyltrimethoxysilane (A-171).
Another object of the present invention is to provide a method for preparing the above soap-free polymeric cationic dispersion, comprising the steps of:
s1, adding glycidyl isocyanurate, acrylic acid, a catalyst and a polymerization inhibitor into a reaction kettle, and heating and stirring for reaction to obtain modified acrylic ester;
s2, adding DMAEMA, an acrylic ester monomer, a styrene monomer, modified acrylic ester, a regulator and an initiator into a reaction kettle under the heating condition by taking alcohol as a solvent, adding a post-treatment initiator and alcohol for reaction, reacting again, cooling, adding a neutralizing agent, and adding water and stirring uniformly to obtain an emulsifier;
s3, adding the emulsifying agent and water into a reaction kettle, adding initial introduction under the heating condition, then adding a polymerization monomer, a silane coupling agent and an initiator, carrying out heat preservation reaction, cooling, adding an oxidant and a reducing agent, and discharging to obtain the soap-free polymerized cationic dispersion.
Further, in the step S1, the temperature of the heating and stirring reaction is 80-120 ℃ and the time is 0.5-6h.
Further, the molar ratio of the glycidyl isocyanurate to the acrylic acid is 1 (3-5).
Further, the mass ratio of the DMAEMA to the acrylic ester monomer to the styrene monomer to the modified acrylic ester to the regulator is (100-300)/(800-1200)/(300-500)/(50-200)/(10-20).
Further, the regulator is n-dodecyl mercaptan (NDM).
Further, in step S2, the heating temperature is 70-80 ℃, the reaction time is 30-90min, and the re-reaction time is 30-90min.
Further, in the step S3, the heating temperature is 80-90 ℃, and the time of the heat preservation reaction is 30-90min.
The invention has the following beneficial effects:
in the soap-free polymerized cationic dispersion provided by the invention, DMAEMA, acrylic ester, styrene and modified acrylic ester are firstly adopted as monomers to react to obtain the emulsifier, and the DMAEMA is introduced to enable the emulsifier to have cationic polymer characteristics, so that the compatibility among components of the dispersion is improved, the emulsifying property is better, the subsequent polymerization of the monomers is facilitated to react to obtain an ideal polymer, and the ideal polymer is easier to crosslink with tannic acid in wood, so that good blocking and sealing tannic acid effects are realized, and the tannic acid prevention and contamination resistance of the dispersion coating are also enhanced along with the increase of the consumption of the DMAEMA; in addition, as triglycidyl isocyanurate modified acrylic ester is introduced into the emulsifier, the emulsifier has a larger molecular weight and a more three-dimensional net-shaped branched structure, further improves the emulsifying property on the basis of DMAEMA, can stably adsorb on the particle surface in emulsion, avoids aggregation and precipitation, and obviously enhances the adhesive force and stability of dispersion coating.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are set forth. The starting materials, reactions and workup procedures used in the examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.
The words "preferred," "more preferred," and the like in the present disclosure refer to embodiments of the present disclosure that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It should be understood that, except in any operating examples, or where otherwise indicated, quantities or all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.
The initiator in the examples of the present invention is Azobisisobutyronitrile (AIBN).
The FF6M brand in the embodiment of the invention is
In the embodiment of the invention, "parts" refer to parts by weight.
Example 1
The soap-free polymerized cationic dispersion is prepared from the following components in parts by mass:
the preparation method of the soap-free polymerized cationic dispersion comprises the following steps:
s1, adding glycidyl isocyanurate and acrylic acid in a molar ratio of 1:3 into a reaction kettle, simultaneously adding triethylamine and para-hydroxyanisole (the triethylamine is 0.3wt% of the acrylic acid and the para-hydroxyanisole is 0.5wt% of the acrylic acid), heating to 90 ℃ and stirring for reaction for 1h, then heating to 100 ℃ for reaction for 1h, then heating to 115 ℃, and reacting until the acid value is lower than 5mgKOH/g and the epoxy value is lower than 0.02 equivalent/100 g to obtain modified acrylic ester;
s2, mixing 450 parts of methyl methacrylate, 465 parts of butyl acrylate, 325 parts of styrene, 80 parts of modified acrylic ester, 100 parts of DMAEMA, 18 parts of n-dodecyl mercaptan and 36 parts of initiator to obtain a mixed solution 1;
adding 480 parts of absolute ethyl alcohol into a reaction kettle, heating to 78 ℃, dropwise adding the mixed solution 1 within 240min, performing heat preservation reaction for 60min, and then dropwise adding a mixed solution of 5 parts of initiator and 120 parts of absolute ethyl alcohol within 60min, performing heat preservation reaction for 60min; cooling to 50 ℃, adding 84 parts of acetic acid for neutralization, then adding 2643 parts of deionized water, and uniformly stirring to obtain an emulsifier;
s3, adding 0.5 part of initiator into 10 parts of deionized water to obtain initial priming;
166 parts of methyl methacrylate, 100 parts of butyl acrylate, 60 parts of 2-ethylhexyl acrylate, 2 parts of trimethylolpropane trimethacrylate, 10 parts of 2-hydroxyethyl acrylate and 4 parts of vinyl trimethoxysilane are mixed to obtain a mixed solution 2;
adding 1 part of tert-butyl peroxide into 10 parts of deionized water to obtain an oxidant solution; adding 0.6 part of FF6M into 10 parts of deionized water to obtain a reducer solution;
adding 700 parts of the emulsifying agent and 480 parts of deionized water into a reaction kettle, heating to 82 ℃, adding 10.5 parts of primary introduction, preserving heat for 5min, then simultaneously dropwise adding the mixed solution of the mixed solution 2, 1.2 parts of the initiator and 50 parts of deionized water within 180min, and carrying out heat preservation reaction for 60min; and cooling to 60 ℃, simultaneously dropwise adding an oxidant solution and a reducing agent solution within 30min, uniformly stirring, cooling to room temperature, and discharging to obtain the soap-free polymerized cation dispersoid.
Example 2
The soap-free polymerized cationic dispersion is prepared from the following components in parts by mass:
the preparation method of the soap-free polymerized cationic dispersion comprises the following steps:
s1, adding glycidyl isocyanurate and acrylic acid in a molar ratio of 1:3 into a reaction kettle, simultaneously adding triethylamine and para-hydroxyanisole (the triethylamine is 0.3wt% of the acrylic acid and the para-hydroxyanisole is 0.5wt% of the acrylic acid), heating to 90 ℃ and stirring for reaction for 1h, then heating to 100 ℃ for reaction for 1h, then heating to 115 ℃, and reacting until the acid value is lower than 5mgKOH/g and the epoxy value is lower than 0.02 equivalent/100 g to obtain modified acrylic ester;
s2, mixing 450 parts of methyl methacrylate, 465 parts of butyl acrylate, 325 parts of styrene, 80 parts of modified acrylic ester, 130 parts of DMAEMA, 18 parts of n-dodecyl mercaptan and 36 parts of initiator to obtain a mixed solution 1;
adding 480 parts of absolute ethyl alcohol into a reaction kettle, heating to 78 ℃, dropwise adding the mixed solution 1 within 240min, performing heat preservation reaction for 60min, and then dropwise adding a mixed solution of 5 parts of initiator and 120 parts of absolute ethyl alcohol within 60min, performing heat preservation reaction for 60min; cooling to 50 ℃, adding 84 parts of acetic acid for neutralization, then adding 2643 parts of deionized water, and uniformly stirring to obtain an emulsifier;
s3, adding 0.5 part of initiator into 10 parts of deionized water to obtain initial priming;
166 parts of methyl methacrylate, 100 parts of butyl acrylate, 60 parts of 2-ethylhexyl acrylate, 2 parts of trimethylolpropane trimethacrylate, 10 parts of 2-hydroxyethyl acrylate and 4 parts of vinyl trimethoxysilane are mixed to obtain a mixed solution 2;
adding 1 part of tert-butyl peroxide into 10 parts of deionized water to obtain an oxidant solution; adding 0.6 part of FF6M into 10 parts of deionized water to obtain a reducer solution;
adding 700 parts of the emulsifying agent and 480 parts of deionized water into a reaction kettle, heating to 82 ℃, adding 10.5 parts of primary introduction, preserving heat for 5min, then simultaneously dropwise adding the mixed solution of the mixed solution 2, 1.2 parts of the initiator and 50 parts of deionized water within 180min, and carrying out heat preservation reaction for 60min; and cooling to 60 ℃, simultaneously dropwise adding an oxidant solution and a reducing agent solution within 30min, uniformly stirring, cooling to room temperature, and discharging to obtain the soap-free polymerized cation dispersoid.
Example 3
The soap-free polymerized cationic dispersion is prepared from the following components in parts by mass:
the preparation method of the soap-free polymerized cationic dispersion comprises the following steps:
s1, adding glycidyl isocyanurate and acrylic acid in a molar ratio of 1:3 into a reaction kettle, simultaneously adding triethylamine and para-hydroxyanisole (the triethylamine is 0.3wt% of the acrylic acid and the para-hydroxyanisole is 0.5wt% of the acrylic acid), heating to 90 ℃ and stirring for reaction for 1h, then heating to 100 ℃ for reaction for 1h, then heating to 115 ℃, and reacting until the acid value is lower than 5mgKOH/g and the epoxy value is lower than 0.02 equivalent/100 g to obtain modified acrylic ester;
s2, mixing 450 parts of methyl methacrylate, 465 parts of butyl acrylate, 325 parts of styrene, 80 parts of modified acrylic ester, 160 parts of DMAEMA, 18 parts of n-dodecyl mercaptan and 36 parts of initiator to obtain a mixed solution 1;
adding 480 parts of absolute ethyl alcohol into a reaction kettle, heating to 78 ℃, dropwise adding the mixed solution 1 within 240min, performing heat preservation reaction for 60min, and then dropwise adding a mixed solution of 5 parts of initiator and 120 parts of absolute ethyl alcohol within 60min, performing heat preservation reaction for 60min; cooling to 50 ℃, adding 84 parts of acetic acid for neutralization, then adding 2643 parts of deionized water, and uniformly stirring to obtain an emulsifier;
s3, adding 0.5 part of initiator into 10 parts of deionized water to obtain initial priming;
166 parts of methyl methacrylate, 100 parts of butyl acrylate, 60 parts of 2-ethylhexyl acrylate, 2 parts of trimethylolpropane trimethacrylate, 10 parts of 2-hydroxyethyl acrylate and 4 parts of vinyl trimethoxysilane are mixed to obtain a mixed solution 2;
adding 1 part of tert-butyl peroxide into 10 parts of deionized water to obtain an oxidant solution; adding 0.6 part of FF6M into 10 parts of deionized water to obtain a reducer solution;
adding 700 parts of the emulsifying agent and 480 parts of deionized water into a reaction kettle, heating to 82 ℃, adding 10.5 parts of primary introduction, preserving heat for 5min, then simultaneously dropwise adding the mixed solution of the mixed solution 2, 1.2 parts of the initiator and 50 parts of deionized water within 180min, and carrying out heat preservation reaction for 60min; and cooling to 60 ℃, simultaneously dropwise adding an oxidant solution and a reducing agent solution within 30min, uniformly stirring, cooling to room temperature, and discharging to obtain the soap-free polymerized cation dispersoid.
Example 4
The soap-free polymerized cationic dispersion is prepared from the following components in parts by mass:
the preparation method of the soap-free polymerized cationic dispersion comprises the following steps:
s1, adding glycidyl isocyanurate and acrylic acid in a molar ratio of 1:3 into a reaction kettle, simultaneously adding triethylamine and para-hydroxyanisole (the triethylamine is 0.3wt% of the acrylic acid and the para-hydroxyanisole is 0.5wt% of the acrylic acid), heating to 90 ℃ and stirring for reaction for 1h, then heating to 100 ℃ for reaction for 1h, then heating to 115 ℃, and reacting until the acid value is lower than 5mgKOH/g and the epoxy value is lower than 0.02 equivalent/100 g to obtain modified acrylic ester;
s2, mixing 450 parts of methyl methacrylate, 465 parts of butyl acrylate, 325 parts of styrene, 80 parts of modified acrylic ester, 200 parts of DMAEMA, 18 parts of n-dodecyl mercaptan and 36 parts of initiator to obtain a mixed solution 1;
adding 480 parts of absolute ethyl alcohol into a reaction kettle, heating to 78 ℃, dropwise adding the mixed solution 1 within 240min, performing heat preservation reaction for 60min, and then dropwise adding a mixed solution of 5 parts of initiator and 120 parts of absolute ethyl alcohol within 60min, performing heat preservation reaction for 60min; cooling to 50 ℃, adding 84 parts of acetic acid for neutralization, then adding 2643 parts of deionized water, and uniformly stirring to obtain an emulsifier;
s3, adding 0.5 part of initiator into 10 parts of deionized water to obtain initial priming;
166 parts of methyl methacrylate, 100 parts of butyl acrylate, 60 parts of 2-ethylhexyl acrylate, 2 parts of trimethylolpropane trimethacrylate, 10 parts of 2-hydroxyethyl acrylate and 4 parts of vinyl trimethoxysilane are mixed to obtain a mixed solution 2;
adding 1 part of tert-butyl peroxide into 10 parts of deionized water to obtain an oxidant solution; adding 0.6 part of FF6M into 10 parts of deionized water to obtain a reducer solution;
adding 700 parts of the emulsifying agent and 480 parts of deionized water into a reaction kettle, heating to 82 ℃, adding 10.5 parts of primary introduction, preserving heat for 5min, then simultaneously dropwise adding the mixed solution of the mixed solution 2, 1.2 parts of the initiator and 50 parts of deionized water within 180min, and carrying out heat preservation reaction for 60min; and cooling to 60 ℃, simultaneously dropwise adding an oxidant solution and a reducing agent solution within 30min, uniformly stirring, cooling to room temperature, and discharging to obtain the soap-free polymerized cation dispersoid.
Example 5
The soap-free polymerized cationic dispersion is prepared from the following components in parts by mass:
the preparation method of the soap-free polymerized cationic dispersion comprises the following steps:
s1, adding glycidyl isocyanurate and acrylic acid in a molar ratio of 1:3 into a reaction kettle, simultaneously adding triethylamine and para-hydroxyanisole (the triethylamine is 0.3wt% of the acrylic acid and the para-hydroxyanisole is 0.5wt% of the acrylic acid), heating to 90 ℃ and stirring for reaction for 1h, then heating to 100 ℃ for reaction for 1h, then heating to 115 ℃, and reacting until the acid value is lower than 5mgKOH/g and the epoxy value is lower than 0.02 equivalent/100 g to obtain modified acrylic ester;
s2, mixing 450 parts of methyl methacrylate, 465 parts of butyl acrylate, 325 parts of styrene, 80 parts of modified acrylic ester, 220 parts of DMAEMA, 18 parts of n-dodecyl mercaptan and 36 parts of initiator to obtain a mixed solution 1;
adding 480 parts of absolute ethyl alcohol into a reaction kettle, heating to 78 ℃, dropwise adding the mixed solution 1 within 240min, performing heat preservation reaction for 60min, and then dropwise adding a mixed solution of 5 parts of initiator and 120 parts of absolute ethyl alcohol within 60min, performing heat preservation reaction for 60min; cooling to 50 ℃, adding 84 parts of acetic acid for neutralization, then adding 2643 parts of deionized water, and uniformly stirring to obtain an emulsifier;
s3, adding 0.5 part of initiator into 10 parts of deionized water to obtain initial priming;
166 parts of methyl methacrylate, 100 parts of butyl acrylate, 60 parts of 2-ethylhexyl acrylate, 2 parts of trimethylolpropane trimethacrylate, 10 parts of 2-hydroxyethyl acrylate and 4 parts of vinyl trimethoxysilane are mixed to obtain a mixed solution 2;
adding 1 part of tert-butyl peroxide into 10 parts of deionized water to obtain an oxidant solution; adding 0.6 part of FF6M into 10 parts of deionized water to obtain a reducer solution;
adding 700 parts of the emulsifying agent and 480 parts of deionized water into a reaction kettle, heating to 82 ℃, adding 10.5 parts of primary introduction, preserving heat for 5min, then simultaneously dropwise adding the mixed solution of the mixed solution 2, 1.2 parts of the initiator and 50 parts of deionized water within 180min, and carrying out heat preservation reaction for 60min; and cooling to 60 ℃, simultaneously dropwise adding an oxidant solution and a reducing agent solution within 30min, uniformly stirring, cooling to room temperature, and discharging to obtain the soap-free polymerized cation dispersoid.
Example 6
The soap-free polymerized cationic dispersion is prepared from the following components in parts by mass:
the preparation method of the soap-free polymerized cationic dispersion comprises the following steps:
s1, adding glycidyl isocyanurate and acrylic acid in a molar ratio of 1:3 into a reaction kettle, simultaneously adding triethylamine and para-hydroxyanisole (the triethylamine is 0.3wt% of the acrylic acid and the para-hydroxyanisole is 0.5wt% of the acrylic acid), heating to 90 ℃ and stirring for reaction for 1h, then heating to 100 ℃ for reaction for 1h, then heating to 115 ℃, and reacting until the acid value is lower than 5mgKOH/g and the epoxy value is lower than 0.02 equivalent/100 g to obtain modified acrylic ester;
s2, mixing 450 parts of methyl methacrylate, 465 parts of butyl acrylate, 325 parts of styrene, 80 parts of modified acrylic ester, 260 parts of DMAEMA, 18 parts of n-dodecyl mercaptan and 36 parts of initiator to obtain a mixed solution 1;
adding 480 parts of absolute ethyl alcohol into a reaction kettle, heating to 78 ℃, dropwise adding the mixed solution 1 within 240min, performing heat preservation reaction for 60min, and then dropwise adding a mixed solution of 5 parts of initiator and 120 parts of absolute ethyl alcohol within 60min, performing heat preservation reaction for 60min; cooling to 50 ℃, adding 84 parts of acetic acid for neutralization, then adding 2643 parts of deionized water, and uniformly stirring to obtain an emulsifier;
s3, adding 0.5 part of initiator into 10 parts of deionized water to obtain initial priming;
166 parts of methyl methacrylate, 100 parts of butyl acrylate, 60 parts of 2-ethylhexyl acrylate, 2 parts of trimethylolpropane trimethacrylate, 10 parts of 2-hydroxyethyl acrylate and 4 parts of vinyl trimethoxysilane are mixed to obtain a mixed solution 2;
adding 1 part of tert-butyl peroxide into 10 parts of deionized water to obtain an oxidant solution; adding 0.6 part of FF6M into 10 parts of deionized water to obtain a reducer solution;
adding 700 parts of the emulsifying agent and 480 parts of deionized water into a reaction kettle, heating to 82 ℃, adding 10.5 parts of primary introduction, preserving heat for 5min, then simultaneously dropwise adding the mixed solution of the mixed solution 2, 1.2 parts of the initiator and 50 parts of deionized water within 180min, and carrying out heat preservation reaction for 60min; and cooling to 60 ℃, simultaneously dropwise adding an oxidant solution and a reducing agent solution within 30min, uniformly stirring, cooling to room temperature, and discharging to obtain the soap-free polymerized cation dispersoid.
Comparative example 1
The soap-free polymeric cationic dispersion differs from example 1 in that: in the step S2, the modified acrylic ester is replaced by methyl methacrylate with the same mass parts, and other components and preparation methods are the same as those of the example 1.
Comparative example 2
The soap-free polymeric cationic dispersion differs from example 1 in that: in the step S2, methyl methacrylate with equal mass parts is used for replacing DMAEMA, and other components and preparation methods are the same as in the example 1.
Test case
The testing method comprises the following steps:
performance tests were carried out on the soap-free polymeric cationic dispersions prepared in examples 1-6 and comparative examples 1-2.
The testing method comprises the following steps:
stain resistance: the test was performed using HG/T5065-2016 Standard for finishing varnish for architectural coating.
Tannic acid resistance: taking commercially available oak boards with the same size, dividing into 8 groups, respectively adopting the soap-free polymeric cationic dispersion prepared in examples 1-6 or comparative examples 1-2 to spray once, self-drying for 2 hours, polishing, performing secondary spraying, self-drying maintenance for 7d, and then spraying a white finish paint and self-drying for 7d. Two plates are prepared in parallel for each group, one plate is naturally stored at room temperature, and the other plate is placed in an oven at 80 ℃ for 7d at an accelerated speed, and the plates are taken out for comparison and test of chromatic aberration.
Stability: the soap-free polymeric cationic dispersions prepared in examples and comparative examples were each sampled 500mL, filled in a transparent container and sealed, left in an oven at 45 ℃ for 30 days, and then observed for appearance change.
The test results are shown in Table 1.
TABLE 1 Performance test results
Sample of | Stain resistance/% | ΔE | Stability of |
Example 1 | 10.2 | 5 | No precipitate |
Example 2 | 8.3 | 3.5 | No precipitate |
Example 3 | 6.5 | 2.3 | No precipitate |
Example 4 | 5.1 | 1.1 | No precipitate |
Example 5 | 5.0 | 0.5 | No precipitate |
Example 6 | 5.0 | 0.5 | No precipitate |
Comparative example 1 | 14.5 | 10.8 | Precipitation |
Comparative example 2 | 20.2 | 14.4 | Small amount of precipitate |
As can be seen from Table 1, the soap-free polymeric cationic dispersions prepared in examples 1-6 have stain resistance far lower than the national standard of 15 or less, and a delta E as low as 0.5, can achieve almost no chromatic aberration, have no precipitation in high temperature environment, and have excellent stain resistance, tannic acid resistance and stability; and as the consumption of DMAEMA increases, the cationic property of the dispersion is stronger, the anti-contamination and anti-tannic acid effects are better, and the anti-contamination and anti-tannic acid effects are optimal after the consumption of DMAEMA reaches a certain degree. The emulsifier in comparative examples 1-2 has obviously reduced performance due to the replacement of DMAEMA or modified acrylic ester, and proves that the emulsifier is synthesized by adopting DMAEMA, acrylic ester monomer, styrene monomer and triglycidyl isocyanurate modified acrylic ester as raw materials, has obvious promotion effect on the performance of the product, and has a certain synergistic effect among various components.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. The soap-free polymeric cationic dispersion is characterized by being prepared from the following components in parts by mass:
water;
wherein,
the emulsifier is obtained by reacting DMAEMA, an acrylic ester monomer, a styrene monomer and modified acrylic ester;
the modified acrylic ester is obtained by reacting triglycidyl isocyanurate with acrylic acid.
2. The soap-free polymeric cationic dispersion of claim 1 wherein the acrylate monomer is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate.
3. The soap-free polymeric cationic dispersion of claim 1 wherein the polymeric monomer is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.
4. A soap-free polymeric cationic dispersion according to claim 3 wherein said polymeric monomers are methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, trimethylolpropane trimethacrylate and 2-hydroxyethyl acrylate.
5. The soap-free polymeric cationic dispersion according to claim 1 wherein said initial introduction is an initiator solution having a concentration of 1-10%.
6. The soap-free polymeric cationic dispersion according to claim 1 wherein said oxidizing agent is t-butanol peroxide.
7. A process for the preparation of a soap-free polymeric cationic dispersion as claimed in any one of claims 1 to 6 wherein said process for the preparation of a soap-free polymeric cationic dispersion comprises the steps of:
s1, adding glycidyl isocyanurate, acrylic acid, a catalyst and a polymerization inhibitor into a reaction kettle, and heating and stirring for reaction to obtain modified acrylic ester;
s2, adding DMAEMA, an acrylic ester monomer, a styrene monomer, modified acrylic ester, a regulator and an initiator into a reaction kettle under the heating condition by taking alcohol as a solvent, adding a post-treatment initiator and alcohol for reaction, reacting again, cooling, adding a neutralizing agent, and adding water and stirring uniformly to obtain an emulsifier;
s3, adding the emulsifying agent and water into a reaction kettle, adding initial introduction under the heating condition, then adding a polymerization monomer, a silane coupling agent and an initiator, carrying out heat preservation reaction, cooling, adding an oxidant and a reducing agent, and discharging to obtain the soap-free polymerized cationic dispersion.
8. The process for preparing a soap-free polymeric cationic dispersion according to claim 7 wherein in step S1, the temperature of the heating and stirring reaction is 80 to 120 ℃ for 0.5 to 6 hours.
9. The process for preparing a soap-free polymeric cationic dispersion according to claim 7 wherein in step S2 said heating is at a temperature of 70-80 ℃, said reacting is for a period of 30-90min and said re-reacting is for a period of 30-90min.
10. The process for preparing a soap-free polymeric cationic dispersion according to claim 7 wherein in step S3 said heating is carried out at a temperature of 80 to 90 ℃ and said incubation is carried out for a period of 30 to 90 minutes.
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