CN117946350B - Normal-temperature-cured aqueous acrylic resin emulsion - Google Patents
Normal-temperature-cured aqueous acrylic resin emulsion Download PDFInfo
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- CN117946350B CN117946350B CN202410357431.7A CN202410357431A CN117946350B CN 117946350 B CN117946350 B CN 117946350B CN 202410357431 A CN202410357431 A CN 202410357431A CN 117946350 B CN117946350 B CN 117946350B
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- 239000000839 emulsion Substances 0.000 title claims abstract description 76
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 57
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 47
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- -1 acrylic ester Chemical class 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical group OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 13
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- XPFCZYUVICHKDS-UHFFFAOYSA-N 3-methylbutane-1,3-diol Chemical compound CC(C)(O)CCO XPFCZYUVICHKDS-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229960002887 deanol Drugs 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- KNENSDLFTGIERH-UHFFFAOYSA-N 2,2,4,4-tetramethyl-3-phenylpentan-3-ol Chemical compound CC(C)(C)C(O)(C(C)(C)C)C1=CC=CC=C1 KNENSDLFTGIERH-UHFFFAOYSA-N 0.000 claims description 8
- AAJGISIJWYVWOG-UHFFFAOYSA-L iron(2+);2-[2-[(2-oxidophenyl)methylideneamino]ethyliminomethyl]phenolate Chemical compound [Fe+2].[O-]C1=CC=CC=C1C=NCCN=CC1=CC=CC=C1[O-] AAJGISIJWYVWOG-UHFFFAOYSA-L 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- HUOBWFKCWUVATL-UHFFFAOYSA-N 1-butyl-2-ethenylbenzene Chemical compound CCCCC1=CC=CC=C1C=C HUOBWFKCWUVATL-UHFFFAOYSA-N 0.000 claims description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 2
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- BHKAWXZKFKVZLK-UHFFFAOYSA-N 2,3-ditert-butyl-6-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(C(C)(C)C)=C1O BHKAWXZKFKVZLK-UHFFFAOYSA-N 0.000 claims 1
- AAJGISIJWYVWOG-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol iron(2+) Chemical compound [Fe+2].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O AAJGISIJWYVWOG-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 26
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000012948 isocyanate Substances 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 12
- 239000003973 paint Substances 0.000 description 9
- 239000005028 tinplate Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920000616 Poly(1,4-butylene adipate) Polymers 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 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 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to the technical field of coatings, in particular to a normal-temperature-cured aqueous acrylic resin emulsion. The invention relates to a normal-temperature-cured aqueous acrylic resin emulsion, which comprises the following preparation raw materials in parts by weight: 10-15 parts of acrylic acid monomer, 80-120 parts of acrylic ester monomer, 15-25 parts of hydroxyl functional monomer, 3-5 parts of benzene-containing vinyl monomer, 20-30 parts of unsaturated polyester dispersion, 3-5 parts of emulsifier, 0.5-1.5 parts of initiator and 105-160 parts of deionized water; the hydroxyl functional monomer is a mixture of tertiary hydroxyl acrylate and hydroxypropyl methacrylate in a weight ratio of 5-10:10-15. The aqueous acrylic resin emulsion cured at normal temperature has good stability, can be stored for six months without layering at normal temperature, and has excellent adhesive force and water resistance when being matched with a commercially available aqueous isocyanate curing agent for use, thus having wide application prospect.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a normal-temperature-cured aqueous acrylic resin emulsion.
Background
Along with the increasing living standard of people, the requirements on environment protection are gradually increased, the traditional solvent type paint is gradually replaced by environment-friendly paint, the water-based paint is one of the environment-friendly paint, water is used as a dispersion medium, the dosage of organic solvents is greatly reduced, and a solid foundation is laid for the development of the paint industry towards the green and environment-friendly direction.
The aqueous acrylic resin is mainly prepared by copolymerizing acrylic acid, methacrylic acid and ester monomers thereof with other vinyl monomers, and has carbon-carbon bonds on a main chain and various ester bonds on side groups, so that excellent performance can be provided for the aqueous acrylic resin. Depending on the structure on the pendant aqueous acrylic resin, it can be classified into thermoplastic acrylic resins and thermosetting acrylic resins. Thermosetting acrylic resin, also called reactive acrylic resin, has crosslinking group in its molecular structure, and under certain condition, the insoluble and infusible crosslinked polymer with bodily structure is produced through the crosslinking reaction between the active group in the polymer molecular chain and the externally added crosslinking agent or through the chemical reaction between the active groups in the polymer molecular chain. The hydroxy acrylic resin is a typical thermosetting acrylic resin.
The invention discloses a high-solid low-viscosity hydroxyl acrylic resin and a preparation process thereof, which are disclosed in patent technical document CN201010255397.0, wherein the solid content of the hydroxyl acrylic resin obtained by the invention can reach 65-75%, and the viscosity is only 1000-2500mps. The solvent used in the process is low in price, expensive high-boiling point solvent is not needed, the preparation process is simple, and the production cost is low. However, the hydroxy acrylic resin prepared by the method is still in a linear molecular structure, intermolecular entanglement is unavoidable, the viscosity is too high when the solid content is high, and a large amount of organic solvent is needed to be added for dilution during construction.
Patent technical document CN202011613395.4 is a hydroxy acrylic resin emulsion, and a preparation method and application thereof, wherein the hydroxy acrylic resin emulsion comprises the following raw materials: a combination of trimellitic anhydride, a first hydroxyl-containing acrylic acid, a mixed monomer, an initiator, and a chain transfer agent; the finally obtained hydroxy acrylic resin has more branched structures and lower viscosity, and is beneficial to improving the solid content of the hydroxy acrylic resin emulsion; however, the hydroxyl content in the invention is low, the improvement of the crosslinking density of the emulsion is limited, and the compactness, the adhesive force and other properties of the coating are affected to a certain extent.
Disclosure of Invention
Therefore, the invention aims to provide a normal-temperature-cured aqueous acrylic resin emulsion to solve the problem of poor coating performance caused by low hydroxyl content of the traditional aqueous acrylic resin emulsion.
Based on the above purpose, the invention provides a normal temperature solidified aqueous acrylic resin emulsion, which is prepared from the following raw materials in parts by weight: 10-15 parts of acrylic acid monomer, 80-120 parts of acrylic ester monomer, 15-25 parts of hydroxyl functional monomer, 3-5 parts of benzene-containing vinyl monomer, 20-30 parts of unsaturated polyester dispersion, 3-5 parts of emulsifier, 0.5-1.5 parts of initiator and 105-160 parts of deionized water;
The hydroxyl functional monomer is a mixture of tertiary hydroxyl acrylic ester and hydroxypropyl methacrylate in a weight ratio of 5-10:10-15;
The preparation method of the unsaturated polyester dispersion comprises the following steps: adding poly (1, 4-butanediol adipate), methyl methacrylate and p-toluenesulfonic acid into toluene, reacting for 6-8h at 110-120 ℃, then performing reduced pressure distillation, adding triethylamine to adjust the pH to 8-9, adding hydroxyethyl methacrylate and deionized water, and stirring for 30-40min to obtain an unsaturated polyester dispersion with the solid content of 50-60%;
The weight ratio of the poly (1, 4-butanediol adipate), the methyl methacrylate, the p-toluenesulfonic acid, the toluene and the hydroxyethyl methacrylate is 10-15:3-4:0.5-1:30-50:2-2.8;
The tertiary hydroxyl-containing acrylic ester is obtained by the transesterification of isoprene glycol and methyl methacrylate;
Preferably, the average molecular weight of the poly (1, 4-butylene adipate) is 2000.
Preferably, the acrylic monomer is one or a mixture of methacrylic acid and acrylic acid.
Preferably, the acrylate monomer is a mixture of a hard acrylate monomer and a soft acrylate monomer.
Preferably, the hard acrylate monomer is one of methyl methacrylate and butyl methacrylate.
Preferably, the soft acrylate monomer is one of methyl acrylate and butyl acrylate.
Preferably, the benzene-containing vinyl monomer is one or a mixture of more than two of styrene, 2-methyl styrene, 4-methyl styrene, 2-butyl styrene and 4-butyl styrene.
Preferably, the preparation method of the tertiary hydroxyl-containing acrylate comprises the following steps: the method comprises the steps of mixing isoprene glycol, methyl methacrylate, di-tert-butyl hydroxy toluene and N, N' -bis (salicylidene) ethylenediamine iron (II), reacting for 10-14h at 100-110 ℃, and purifying to obtain the tertiary hydroxy acrylate.
Preferably, the weight ratio of the isoprene glycol, the methyl methacrylate, the di-tert-butyl hydroxy toluene and the N, N' -bis (salicylidene) ethylenediamine iron (II) is 10-15:27-38:2.8-4.1:0.3-0.4.
Preferably, the emulsifier is a mixture of anionic surfactant and nonionic surfactant in a weight ratio of 2-3.5:1-1.5.
Preferably, the anionic surfactant is one of sodium dodecyl sulfate, sodium hexadecyl sulfate and sodium dodecyl benzene sulfonate.
Preferably, the nonionic surfactant is alkylphenol ethoxylates.
Preferably, the initiator is azobisisobutyrimidine hydrochloride.
Further, the invention also provides a preparation method of the normal-temperature-cured aqueous acrylic ester emulsion, which comprises the following specific steps:
s1: adding an emulsifier into deionized water under nitrogen atmosphere, stirring and dissolving, then adding an acrylic monomer, an acrylic ester monomer, a hydroxyl functional monomer, a benzene-containing vinyl monomer and an unsaturated polyester dispersion, and stirring and emulsifying for 30-50min to obtain a pre-emulsion;
S2: taking out half of the pre-emulsion, adding half of the initiator, reacting for 2-3 hours at 70-80 ℃, then adding the other half of the pre-emulsion and half of the initiator, reacting for 6-8 hours at 70-80 ℃, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8-9 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion cured at normal temperature.
The invention has the beneficial effects that:
(1) According to the normal-temperature-cured aqueous acrylic resin emulsion, through adding two different hydroxyl functional monomers, the speed of the pre-curing stage is moderate, and a stepped curing process is presented, so that the prepared coating has high compactness, and the water resistance is further improved.
(2) According to the normal-temperature-cured aqueous acrylic resin emulsion, the hydroxyethyl methacrylate is loaded in the unsaturated polyester latex, so that the crosslinking density is further improved, the problems of gel and poor storage stability caused by high hydroxyl content are avoided, and the water resistance and the adhesive force of the coating are improved.
(3) The aqueous acrylic resin emulsion cured at normal temperature can be stored for a long time, and when the aqueous acrylic resin emulsion is matched with a commercially available aqueous isocyanate curing agent for use, the obtained coating has excellent adhesive force and water resistance.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The sources or properties of the raw materials used in the examples and comparative examples of the present invention are as follows:
Hydroxyethyl methacrylate is purchased from Shanghai Ala Biochemical technology Co., ltd, under the product number H103044;
hydroxypropyl methacrylate was purchased from Shanghai Ala Biochemical technologies Co., ltd and under the product number H109880.
Example 1: the preparation method of the normal-temperature-cured aqueous acrylic resin emulsion comprises the following specific preparation steps:
(1) 10g of isoprene glycol, 27g of methyl methacrylate, 2.8g of di-tert-butyl hydroxy toluene and 0.3g of N, N' -bis (salicylidene) ethylenediamine iron (II) are mixed, reacted for 10 hours at 100 ℃, and purified to obtain tertiary hydroxyl-containing acrylic ester;
(2) Mixing 5g of acrylate containing tertiary hydroxyl and 10g of hydroxypropyl methacrylate, and uniformly stirring to obtain a hydroxyl functional monomer;
(3) 10g of poly (1, 4-butylene glycol) adipate, 3g of methyl methacrylate and 0.5g of p-toluenesulfonic acid are added into 30g of toluene to react for 6 hours at 110 ℃, then reduced pressure distillation is carried out, triethylamine is added to adjust the pH to 8.2, 2g of hydroxyethyl methacrylate and a proper amount of deionized water are added, and stirring is carried out for 30 minutes, thus obtaining an unsaturated polyester dispersion with 52% of solid content;
(4) Mixing 4g of sodium dodecyl sulfate and 2g of alkylphenol ethoxylates, and uniformly stirring to obtain an emulsifier;
(5) Under nitrogen atmosphere, adding 3g of emulsifier into 105g of deionized water, stirring and dissolving, then adding 10g of acrylic acid, 25g of butyl methacrylate, 55g of butyl acrylate, 15g of hydroxyl functional monomer, 3g of 2-butylstyrene and 20g of unsaturated polyester dispersion, stirring and emulsifying for 30min to obtain pre-emulsion;
(6) Taking out half of the pre-emulsion, adding 0.25g of azobisisobutyronium chloride, reacting for 2 hours at 70 ℃ under nitrogen atmosphere, then adding the other half of the pre-emulsion and 0.25g of azobisisobutyronium chloride, reacting for 6 hours at 70 ℃, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8.1 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion cured at normal temperature.
Example 2: the preparation method of the normal-temperature-cured aqueous acrylic resin emulsion comprises the following specific preparation steps:
(1) 12.5g of isoprene glycol, 33g of methyl methacrylate, 3.5g of di-tert-butyl hydroxy toluene and 0.35g of N, N' -bis (salicylidene) ethylenediamine iron (II) are mixed, reacted for 12 hours at 105 ℃, and purified to obtain tertiary hydroxyl-containing acrylic ester;
(2) 7.5g of acrylate containing tertiary hydroxyl and 12.5g of hydroxypropyl methacrylate are mixed and stirred uniformly to obtain a hydroxyl functional monomer;
(3) Adding 12.5g of poly (1, 4-butylene adipate), 3.5g of methyl methacrylate and 0.75g of p-toluenesulfonic acid into 40g of toluene, reacting for 7 hours at 115 ℃, then carrying out reduced pressure distillation, adding triethylamine to adjust the pH to 8.4, adding 2.4g of hydroxyethyl methacrylate and a proper amount of deionized water, and stirring for 35 minutes to obtain an unsaturated polyester dispersion with the solid content of 56%;
(4) Mixing 5.5g of sodium dodecyl sulfate and 2.5g of alkylphenol ethoxylates, and uniformly stirring to obtain an emulsifier;
(5) Adding 4g of an emulsifier into 130g of deionized water under nitrogen atmosphere, stirring and dissolving, then adding 12.5g of acrylic acid, 35g of butyl methacrylate, 65g of butyl acrylate, 20g of hydroxyl functional monomer, 4g of styrene and 25g of unsaturated polyester dispersion, and stirring and emulsifying for 40min to obtain a pre-emulsion;
(6) Taking out half of the pre-emulsion, adding 0.5g of azobisisobutyronium chloride, reacting at 75 ℃ for 2.5h, then adding the other half of the pre-emulsion and 0.5g of azobisisobutyronium chloride, reacting at 75 ℃ for 7h, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8.5 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion solidified at normal temperature.
Example 3: the preparation method of the normal-temperature-cured aqueous acrylic resin emulsion comprises the following specific preparation steps:
(1) 14g of isoprene glycol, 30g of methyl methacrylate, 4g of di-tert-butyl hydroxy toluene and 0.3g of N, N' -bis (salicylidene) ethylenediamine iron (II) are mixed, reacted for 10 hours at 110 ℃, and purified to obtain tertiary hydroxyl-containing acrylic ester;
(2) 8g of acrylate containing tertiary hydroxyl and 13g of hydroxypropyl methacrylate are mixed and stirred uniformly to obtain a hydroxyl functional monomer;
(3) Adding 12g of poly (1, 4-butylene adipate), 3.3g of methyl methacrylate and 1g of p-toluenesulfonic acid into 50g of toluene, reacting for 6 hours at 120 ℃, then carrying out reduced pressure distillation, adding triethylamine to adjust the pH to 8.8, adding 2.2g of hydroxyethyl methacrylate and a proper amount of deionized water, and stirring for 40 minutes to obtain an unsaturated polyester dispersion with the solid content of 60%;
(4) Mixing 4g of sodium dodecyl sulfate and 3g of alkylphenol ethoxylates, and uniformly stirring to obtain an emulsifier;
(5) Under nitrogen atmosphere, adding 5g of emulsifier into 160g of deionized water, stirring and dissolving, then adding 10g of acrylic acid, 35g of butyl methacrylate, 75g of butyl acrylate, 23g of hydroxyl functional monomer, 4g of 2-methyl styrene and 25g of unsaturated polyester dispersion, stirring and emulsifying for 50min to obtain pre-emulsion;
(6) Taking out half of the pre-emulsion, adding 0.65g of azobisisobutyronitrile hydrochloride, reacting for 2 hours at 70 ℃ under nitrogen atmosphere, then adding the other half of the pre-emulsion and 0.65g of azobisisobutyronimidine hydrochloride, reacting for 8 hours at 80 ℃, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion solidified at normal temperature.
Example 4: the preparation method of the normal-temperature-cured aqueous acrylic resin emulsion comprises the following specific preparation steps:
(1) 15g of isoprene glycol, 38g of methyl methacrylate, 4.1g of di-tert-butyl hydroxy toluene and 0.4g of N, N' -bis (salicylidene) ethylenediamine iron (II) are mixed, reacted for 14 hours at 110 ℃, and purified to obtain tertiary hydroxyl-containing acrylic ester;
(2) 10g of acrylate containing tertiary hydroxyl and 15g of hydroxypropyl methacrylate are mixed and stirred uniformly to obtain a hydroxyl functional monomer;
(3) 15g of poly (1, 4-butylene glycol adipate), 4g of methyl methacrylate and 1g of p-toluenesulfonic acid are added into 50g of toluene to react for 8 hours at 120 ℃, then reduced pressure distillation is carried out, triethylamine is added to adjust the pH to 8, 2.8g of hydroxyethyl methacrylate and a proper amount of deionized water are added, and stirring is carried out for 40 minutes, thus obtaining unsaturated polyester dispersoid with 50% of solid content;
(4) Mixing 7g of sodium dodecyl sulfate and 3g of alkylphenol ethoxylates, and uniformly stirring to obtain an emulsifier;
(5) Under nitrogen atmosphere, adding 5g of emulsifier into 160g of deionized water, stirring and dissolving, then adding 15g of acrylic acid, 40g of butyl methacrylate, 80g of butyl acrylate, 25g of hydroxyl functional monomer, 5g of styrene and 30g of unsaturated polyester dispersion, stirring and emulsifying for 45min to obtain pre-emulsion;
(6) Taking out half of the pre-emulsion, adding 0.75g of azobisisobutyronium chloride, reacting for 2 hours at 77 ℃ under nitrogen atmosphere, then adding the other half of the pre-emulsion and 0.75g of azobisisobutyronium chloride, reacting for 7 hours at 73 ℃, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8.2 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion cured at normal temperature.
Comparative example 1: the preparation method of the aqueous acrylic resin emulsion comprises the following specific steps:
(1) Adding 12.5g of poly (1, 4-butylene adipate), 3.5g of methyl methacrylate and 0.75g of p-toluenesulfonic acid into 40g of toluene, reacting for 7 hours at 115 ℃, then carrying out reduced pressure distillation, adding triethylamine to adjust the pH to 8.4, adding 2.4g of hydroxyethyl methacrylate and a proper amount of deionized water, and stirring for 35 minutes to obtain an unsaturated polyester dispersion with the solid content of 56%;
(2) Mixing 5.5g of sodium dodecyl sulfate and 2.5g of alkylphenol ethoxylates, and uniformly stirring to obtain an emulsifier;
(3) Adding 4g of an emulsifier into 130g of deionized water under nitrogen atmosphere, stirring and dissolving, then adding 12.5g of acrylic acid, 35g of butyl methacrylate, 65g of butyl acrylate, 20g of hydroxypropyl methacrylate, 4g of styrene and 25g of unsaturated polyester dispersion, and stirring and emulsifying for 40min to obtain a pre-emulsion;
(4) Taking out half of the pre-emulsion, adding 0.5g of azobisisobutyronium chloride, reacting at 75 ℃ for 2.5h, then adding the other half of the pre-emulsion and 0.5g of azobisisobutyronium chloride, reacting at 75 ℃ for 7h, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8.5 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion solidified at normal temperature.
Comparative example 2: the preparation method of the aqueous acrylic resin emulsion comprises the following specific steps:
(1) 12.5g of isoprene glycol, 33g of methyl methacrylate, 3.5g of di-tert-butyl hydroxy toluene and 0.35g of N, N' -bis (salicylidene) ethylenediamine iron (II) are mixed, reacted for 12 hours at 105 ℃, and purified to obtain tertiary hydroxyl-containing acrylic ester;
(2) 7.5g of acrylate containing tertiary hydroxyl, 12.5g of hydroxypropyl methacrylate and 2g of hydroxyethyl methacrylate are mixed and stirred uniformly to obtain a hydroxyl functional monomer;
(3) Adding 12.5g of poly (1, 4-butylene adipate), 3.5g of methyl methacrylate and 0.75g of p-toluenesulfonic acid into 40g of toluene, reacting for 7 hours at 115 ℃, then carrying out reduced pressure distillation, adding triethylamine to adjust the pH to 8.4, adding a proper amount of deionized water, and stirring for 35min to obtain an unsaturated polyester dispersion with the solid content of 56%;
(4) Mixing 5.5g of sodium dodecyl sulfate and 2.5g of alkylphenol ethoxylates, and uniformly stirring to obtain an emulsifier;
(5) Adding 4g of an emulsifier into 130g of deionized water under nitrogen atmosphere, stirring and dissolving, then adding 12.5g of acrylic acid, 35g of butyl methacrylate, 65g of butyl acrylate, 22g of hydroxyl functional monomer, 4g of styrene and 25g of unsaturated polyester dispersion, and stirring and emulsifying for 40min to obtain a pre-emulsion;
(6) Taking out half of the pre-emulsion, adding 0.5g of azobisisobutyronium chloride, reacting at 75 ℃ for 2.5h, then adding the other half of the pre-emulsion and 0.5g of azobisisobutyronium chloride, reacting at 75 ℃ for 7h, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8.5 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion solidified at normal temperature.
Comparative example 3: the preparation method of the aqueous acrylic resin emulsion comprises the following specific steps:
(1) Adding 12.5g of poly (1, 4-butylene adipate), 3.5g of methyl methacrylate and 0.75g of p-toluenesulfonic acid into 40g of toluene, reacting for 7 hours at 115 ℃, then carrying out reduced pressure distillation, adding triethylamine to adjust the pH to 8.4, adding a proper amount of deionized water, and stirring for 35min to obtain an unsaturated polyester dispersion with the solid content of 56%;
(2) Mixing 5.5g of sodium dodecyl sulfate and 2.5g of alkylphenol ethoxylates, and uniformly stirring to obtain an emulsifier;
(3) Adding 4g of an emulsifier into 130g of deionized water under nitrogen atmosphere, stirring and dissolving, then adding 12.5g of acrylic acid, 35g of butyl methacrylate, 65g of butyl acrylate, 22g of hydroxypropyl methacrylate, 4g of styrene and 25g of unsaturated polyester dispersion, and stirring and emulsifying for 40min to obtain a pre-emulsion;
(4) Taking out half of the pre-emulsion, adding 0.5g of azobisisobutyronium chloride, reacting at 75 ℃ for 2.5h, then adding the other half of the pre-emulsion and 0.5g of azobisisobutyronium chloride, reacting at 75 ℃ for 7h, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8.5 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion solidified at normal temperature.
Performance testing
Gel fraction: the aqueous acrylic resin emulsions prepared in examples and comparative examples were filtered using a 100 mesh screen, and gel on the screen, stirring slurry and bottle wall were collected, dried in an oven to constant weight and weighed after deionized water rinse, and the gel rate was calculated as follows:
Wherein M is the total mass of the gel after drying;
M1 is the total mass of the aqueous acrylic ester emulsion mixed monomer; the test results are shown in Table 1.
Storage stability: 1.5mL of the aqueous acrylic resin emulsion prepared in the examples and the comparative examples was injected into a 2mL sample tube, and the mixture was stored in a sealed manner; it was stored at room temperature for six months, and the emulsion was observed for the occurrence of delamination, sedimentation, flocculation, etc., and the test results are shown in table 1.
The aqueous acrylic resin emulsions prepared in examples and comparative examples were mixed with an aqueous isocyanate crosslinking agent in a certain ratio to prepare a coating, the coating was uniformly knife-coated on the surface of a polished tin plate, and the coating was left at room temperature for 24 hours, and pencil hardness and adhesion tests were performed on the coating, and the test results are shown in table 2.
Pencil hardness: the hardness of the coating was determined according to GB/T6739-2006 Standard for determination of paint film hardness by the paint and varnish pencil method. The pencil is put into a BY type pencil hardness tester according to national standard, the pencil is pushed forward at the surface of the coating at the speed of 1mm/s for 1cm, and the hardness of the hardest pencil with scratches below 3mm on the surface of the coating is the hardness of the coating.
Adhesion force: the adhesion of the coating was determined according to the standard of GB/T9286-1998 cross-hatch test of color paint and varnish film. Carrying out a cross-cut test on the surface of the coating by using an adhesive force tester, classifying the graphs subjected to cross-cut according to six grades, wherein the adhesive force of grade 0 is highest, and the adhesive force of grade 5 is lowest; the adhesion of the coating to the material was assessed.
Water absorption rate: the water absorption of the coating is tested according to HG/T3856-2006 insulating paint film water absorption measurement method, the coating is uniformly prepared on tinplate, and the coating is placed for 24 hours at room temperature. Weighing the tinplate to m0, immersing the tinplate coated with the coating in specified distilled water after weighing the tinplate to m1, taking out the tinplate after immersing the tinplate in the specified distilled water for 24 hours at normal temperature, sucking the surface moisture by filter paper, immediately weighing the weight of the tinplate to be m2, calculating the water absorption A (%) by the weight difference before and after immersing the tinplate in the distilled water, taking 10 test pieces for measurement, taking the average value, and adopting the calculation formula as follows:
TABLE 1 Water-based acrylate emulsion Performance test results
TABLE 2 coating Performance test results
Data analysis:
As can be seen from examples in tables 1 and 2, the room temperature-curable aqueous acrylic resin emulsion of the present invention has excellent storage stability and a low gel fraction, can be stored for a long period of time, and has excellent water resistance and adhesion to a coating layer obtained by curing it with a commercially available aqueous isocyanate curing agent at room temperature.
As can be seen from examples 2 and 2 of tables 1 and 2, the hydroxyethyl methacrylate is loaded in the latex of the unsaturated polyester, so that on one hand, the curing degree can be further improved, the crosslinking density can be improved, and the water resistance and the adhesive force of the coating can be further improved; meanwhile, the problem of reduced coating density caused by the fact that pores are not separated in the curing process is avoided, and on the other hand, the problems of gel and poor storage stability caused by high hydroxyl content are avoided; it can be seen from example 2 and comparative example 1 that the two hydroxyl functional monomers with different activities are adopted, so that the speed of the pre-curing period is moderate, and the stepped curing process is presented, so that the prepared coating has high compactness and further improves the water resistance.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the invention (including the claims) is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (8)
1. The room-temperature-cured aqueous acrylic resin emulsion is characterized by comprising the following preparation raw materials in parts by weight: 10-15 parts of acrylic acid monomer, 80-120 parts of acrylic ester monomer, 15-25 parts of hydroxyl functional monomer, 3-5 parts of benzene-containing vinyl monomer, 20-30 parts of unsaturated polyester dispersion, 3-5 parts of emulsifier, 0.5-1.5 parts of initiator and 105-160 parts of deionized water, and the specific preparation steps are as follows:
s1: adding an emulsifier into deionized water under nitrogen atmosphere, stirring and dissolving, then adding an acrylic monomer, an acrylic ester monomer, a hydroxyl functional monomer, a benzene-containing vinyl monomer and an unsaturated polyester dispersion, and stirring and emulsifying for 30-50min to obtain a pre-emulsion;
s2: taking out half of the pre-emulsion, adding half of the initiator, reacting for 2-3 hours at 70-80 ℃, then adding the other half of the pre-emulsion and half of the initiator, reacting for 6-8 hours at 70-80 ℃, cooling to room temperature, sieving with a 100-mesh sieve, and adjusting the pH to 8-9 by using dimethylaminoethanol to obtain the water-based acrylic resin emulsion cured at normal temperature;
The hydroxyl functional monomer is a mixture of tertiary hydroxyl acrylic ester and hydroxypropyl methacrylate in a weight ratio of 5-10:10-15;
The preparation method of the unsaturated polyester dispersion comprises the following steps: adding poly (1, 4-butanediol adipate), methyl methacrylate and p-toluenesulfonic acid into toluene, reacting for 6-8h at 110-120 ℃, then performing reduced pressure distillation, adding triethylamine to adjust the pH to 8-9, adding hydroxyethyl methacrylate and deionized water, and stirring for 30-40min to obtain an unsaturated polyester dispersion with the solid content of 50-60%;
The weight ratio of the poly (1, 4-butanediol adipate), the methyl methacrylate, the p-toluenesulfonic acid, the toluene and the hydroxyethyl methacrylate is 10-15:3-4:0.5-1:30-50:2-2.8;
The tertiary hydroxyl-containing acrylic ester is obtained by transesterification of isoprene glycol and methyl methacrylate.
2. The room temperature curable aqueous acrylic resin emulsion of claim 1 wherein the acrylic monomer is one or a mixture of methacrylic acid and acrylic acid.
3. The room temperature curable aqueous acrylic resin emulsion of claim 1 wherein the acrylate monomer is a mixture of hard acrylate monomers and soft acrylate monomers; the hard acrylic ester monomer is one of methyl methacrylate and butyl methacrylate; the soft acrylic ester monomer is one of methyl acrylate and butyl acrylate.
4. The room temperature curable aqueous acrylic resin emulsion according to claim 1, wherein the benzene-containing vinyl monomer is one or a mixture of two or more of styrene, 2-methyl styrene, 4-methyl styrene, 2-butyl styrene, 4-butyl styrene.
5. The room temperature-curable aqueous acrylic resin emulsion according to claim 1, wherein the preparation method of the tertiary hydroxyl group-containing acrylate is as follows: the method comprises the steps of mixing isoprene glycol, methyl methacrylate, di-tert-butyl hydroxy toluene and N, N' -bis (salicylidene) ethylenediamine iron (II), reacting for 10-14h at 100-110 ℃, and purifying to obtain the tertiary hydroxy acrylate.
6. The room temperature curable aqueous acrylic resin emulsion according to claim 5, wherein the weight ratio of isoprene glycol, methyl methacrylate, di-t-butylhydroxytoluene and iron (II) N, N' -bis (salicylidene) ethylenediamine is 10-15:27-38:2.8-4.1:0.3-0.4.
7. The room temperature curable aqueous acrylic resin emulsion according to claim 1, wherein the emulsifier is a mixture of anionic surfactant and nonionic surfactant in a weight ratio of 2-3.5:1-1.5; the initiator is azo diisobutylamidine hydrochloride.
8. The room temperature curable aqueous acrylic resin emulsion according to claim 7, wherein the anionic surfactant is one of sodium dodecyl sulfate, sodium hexadecyl sulfate and sodium dodecyl benzene sulfonate; the nonionic surfactant is alkylphenol polyoxyethylene.
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