CN112778514B

CN112778514B - Compound, aqueous epoxy resin composition containing the same, and coating composition containing the same

Info

Publication number: CN112778514B
Application number: CN201911083949.1A
Authority: CN
Inventors: 林颖瑞; 刘良兴; 林永昇; 吴国宾; 赖一江; 汪奕森; 黄坤源
Original assignee: Chang Chun Plastics Co Ltd
Current assignee: Chang Chun Plastics Co Ltd
Priority date: 2019-11-07
Filing date: 2019-11-07
Publication date: 2023-07-07
Anticipated expiration: 2039-11-07
Also published as: CN112778514A

Abstract

The present invention provides a compound having an EO (ethylene oxide)/PO (propylene oxide) block copolymer, which is useful as an emulsifier. The invention also provides an aqueous epoxy resin composition comprising the compound and a coating composition comprising the aqueous epoxy resin composition. The invention has the advantages that the epoxy resin composition or the coating composition added with the compound can improve the compatibility between water and epoxy resin and improve the corrosion resistance of the epoxy resin composition and the coating composition.

Description

Compound, aqueous epoxy resin composition containing the same, and coating composition containing the same

Technical Field

The present invention relates to a compound, and an aqueous epoxy resin composition and a coating composition containing the same. More specifically, the present invention relates to a compound having an EO (ethylene oxide)/PO (propylene oxide) block copolymer, and an aqueous epoxy resin composition and a coating composition containing the same.

Background

The epoxy resin composition is widely used in paints, adhesives, laminates, etc. because of its excellent mechanical properties, adhesion properties, etc. as a subsequent product, and it is expected that the market will grow at a stable rate. However, epoxy resins are often diluted with organic solvents to form compositions, which are prone to environmental hazards and do not meet the current environmental awareness of increasing the head.

At present, the water-based epoxy resin using water as a solvent has been developed in the market, and the importance of the water-based epoxy resin is increased because the environmental pollution hazard caused by volatile organic solvents can be reduced, so that the global water-based epoxy resin market has a continuously growing prospect. However, the existing waterborne epoxy resins in the prior art have defects such as water resistance, mechanical stability, corrosion resistance, adhesion with the applied substrate, and the like, and further development of new products is needed to solve the problems.

The aqueous epoxy resin is usually prepared by stirring the aqueous epoxy resin at a high speed in a homomixer by using a surfactant, however, the prepared epoxy resin emulsion has the defects of poor water resistance, poor adhesion with a base material or a finishing paint, low mechanical stability and the like. On the other hand, the conventional art also has a problem that the crosslinking density of the cured product of the epoxy resin composition cannot be improved, and thus the strength and corrosion resistance of the coating film to be applied later are poor.

Disclosure of Invention

The invention aims to provide a compound, an aqueous epoxy resin composition containing the compound and a coating composition containing the aqueous epoxy resin composition, so as to solve the technical problems in the prior art.

The present invention provides a compound comprising the structure of formula (I):

wherein Y represents a cycloaliphatic or aromatic group; x is X ₁ Representation of

Wherein R is ₁ 、R ₂ R is R ₃ At least one or at most two of them are C ₁ To C ₄ Alkyl, the rest is H; x is X ₂ X is X ₃ Middle toAt least one of them is-COOH, or

The rest is H; wherein R is ₄ 、R ₅ R is R ₆ Is H or C ₁ To C ₄ An alkyl group; and a, b, c, d, e and f represent the number of repeating units, and are integers of 1 to 150.

In a preferred embodiment, the aforementioned compound has at least one structure selected from the group consisting of formulas (II) to (VII):

wherein each n independently represents the number of repeating units and is an integer of 5 to 250.

In a preferred embodiment, Y is selected from the group consisting of phthalic anhydride (phthalic acid anhydride), trimellitic anhydride (trimellitic acid anhydride), jiao Midan anhydride (pyromellitic acid anhydride), benzophenone-tetracarboxylic anhydride (hexahydrophthalic acid anhydride), methylhexahydrophthalic anhydride (methylhexahydrophthalic acid anhydride), succinic anhydride (succinic acid anhydride), methylcyclohexene-dicarboxylic anhydride (methylvinylbenzene-dicarboxylic acid anhydride), alkylstyrene-maleic anhydride copolymer (maleic anhydride-maleic anhydride copolymers), chlorobridge anhydride (676), tetrabromophthalic anhydride (methyltetrahydrophthalic acid anhydride), endomethylene tetrahydrophthalic anhydride (endomethylenetetrahydrophthalicacid anhydride), methylendomethylene tetrahydrophthalic anhydride (methylendometylenetetrahydrophthalic acid anhydride), methylbutenyl tetrahydrophthalic anhydride (methylbutenyltetrahydrophthalic acid anhydride), dodecenyl succinic anhydride (dodecenylsuccinic acid anhydride), hexahydrophthalic anhydride (hexahydrophthalic acid anhydride), methylhexahydrophthalic anhydride (methylhexahydrophthalic acid anhydride), succinic anhydride (succinic acid anhydride), methylcyclohexene-dicarboxylic anhydride (methylvinylbenzene-dicarboxylic acid anhydride), alkylstyrene-maleic anhydride copolymer (akyltryene-maleic anhydride copolymers), chlorobenzoic anhydride (673), tetrabromophthalic anhydride (tetrabromophthalic acid anhydride), polyacrylic anhydride (3565), and methacrylic anhydride (methacrylic acid anhydride).

Another object of the present invention is to provide an aqueous epoxy resin composition comprising: (a) an epoxy resin; and (b) a compound as described above.

In a preferred embodiment, (b)/(a) has a ratio in the range of 5% to 15%.

In a preferred embodiment, the epoxy resin has an epoxy equivalent weight of 150 to 3500.

In a preferred embodiment, the epoxy resin has an epoxy equivalent weight of 150 to 650.

In a preferred embodiment, the epoxy resin has an epoxy equivalent weight of 500 to 650.

Another object of the present invention is to provide a coating composition comprising the aqueous epoxy resin composition as described above dispersed in a solvent.

In a preferred embodiment, the coating composition further comprises at least one additive selected from the group consisting of pigments, dyes, defoamers, anti-flash rust agents, rheology modifiers, fillers, extenders, corrosion inhibitors, dispersants, and combinations thereof.

In a preferred embodiment, the coating composition further comprises a curing agent.

In a preferred embodiment, the coating composition has a solids content of 50% to 60%.

In a preferred embodiment, the coating composition has a viscosity in the range of 130cps/25 ℃ to 18000cps/25 ℃.

In a preferred embodiment, the coating composition has a viscosity in the range of 4000cps/25 ℃ to 17000cps/25 ℃.

In a preferred embodiment, the coating composition has a viscosity of greater than 600cps/25 ℃.

In a preferred embodiment, the coating composition has a hardness equal to or greater than grade B as measured by pencil test (ASTM D3363-00).

In a preferred embodiment, the coating composition has an adhesion test (ASTM D3359-09) with a 5B grade adhesion.

In a preferred embodiment, the coating composition has a weight loss of less than 0.36 grams as measured by salt spray testing (ASTM B117).

In a preferred embodiment, the coating composition has a weight loss of less than 0.20 grams as measured by salt spray testing (ASTM B117).

In a preferred embodiment, the coating composition has a weight loss of less than 0.17 grams as measured by salt spray testing (ASTM B117).

Accordingly, it is an object of the present invention to provide a novel compound having a surfactant function, which can be added to an epoxy resin composition as an emulsifier to improve compatibility between water and an epoxy resin, so that an epoxy resin composition comprising the compound has high solubility in water. Accordingly, the present invention further provides an aqueous epoxy resin composition using water as a solvent, and a coating composition comprising the same, which can greatly reduce the content of Volatile Organic Compounds (VOCs), and a coating layer made using the aqueous epoxy resin composition improves surface characteristics, such as: high hardness, good adhesion, good corrosion resistance, and low VOC. On the other hand, the aqueous epoxy resin composition and the coating composition can adjust the viscosity range according to different requirements of later application by selecting the compound with different molecular weights as an emulsifier.

Drawings

FIG. 1A is a flow chart for the synthesis of compound S1.1 according to example 1 of the present invention;

FIG. 1B is a flow chart for synthesizing an aqueous epoxy resin composition S1.2 of example 1 of the present invention;

FIG. 2A is a flow chart for the synthesis of compound S2.1 according to example 2 of the present invention;

FIG. 2B is a flow chart for synthesizing an aqueous epoxy resin composition S2.2 according to example 2 of the present invention;

FIG. 3A is a flow chart for the synthesis of compound S3.1 according to example 3 of the present invention;

FIG. 3B is a flow chart for synthesizing an aqueous epoxy resin composition S3.2 of example 3 of the present invention;

FIG. 4A is a flow chart for the synthesis of compound S4.1 according to example 4 of the present invention;

FIG. 4B is a flow chart for synthesizing the waterborne epoxy resin composition S4.2 of example 4 of the present invention;

FIG. 5A is a flow chart for the synthesis of compound S5.1 according to example 5 of the present invention;

FIG. 5B is a flow chart for synthesizing the aqueous epoxy resin composition S5.2 of example 5 of the present invention;

FIG. 6A is a flow chart for the synthesis of compound S6.1 according to example 6 of the present invention;

FIG. 6B is a flow chart of example 6 of the present invention for synthesizing an aqueous epoxy resin composition S6.2;

FIG. 7A is a flow chart for the synthesis of compound C1.1 according to comparative example 1 of the present invention;

FIG. 7B is a flow chart for synthesizing the aqueous epoxy resin composition C1.2 of comparative example 1 of the present invention;

fig. 8 is a photograph of a sample for corrosion test (test 2) using the samples of examples 1 to 6 and comparative example 1.

Detailed Description

The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.

Wherein R is ₁ 、R ₂ R is R ₃ At least one or at most two of them are C ₁ To C ₄ Alkyl, the rest is H; x is X ₂ X is X ₃ At least one of them is-COOH, or

The rest is H; wherein R is ₄ 、R ₅ R is R ₆ Is H or C ₁ To C ₄ An alkyl group; and a, b, c, d, e and f represent the number of repeating units, and are integers of 1 to 150. The present invention also provides an aqueous epoxy resin composition comprising: (a) an epoxy resin; and (b) a compound as described above. In addition, the invention also provides a coating composition, which comprises the aqueous epoxy resin composition dispersed in a solvent.

Specifically, Y in the foregoing formula (I) may be an acid anhydride having two, three, four or six functional groups per molecule. Anhydrides having two functional groups such as, but not limited to: at least one selected from the group consisting of phthalic anhydride (phthalic acid anhydride), glycerol tribenzoate (glycyl tris-mellitate), maleic anhydride (maleic anhydride), tetrahydrophthalic anhydride (tetrahydrophthalic acid anhydride), methyltetrahydrophthalic anhydride (methyltetrahydrophthalic acid anhydride), endomethylene tetrahydrophthalic anhydride (endomethylenetetrahydrophthalic acid anhydride), methyltetrahydrophthalic anhydride (methylendometylenetetrahydrophthalic acid anhydride), methylbutenyl tetrahydrophthalic anhydride (methylbutenyltetrahydrophthalic acid anhydride), dodecenyl succinic anhydride (dodecenylsuccinic acid anhydride), hexahydrophthalic anhydride (hexahydrophthalic acid anhydride), methylhexahydrophthalic anhydride (methylhexahydrophthalic acid anhydride), succinic anhydride (succinic acid anhydride), methylcyclohexene-dicarboxylic anhydride (methylcylohexene-dicarboxylic acid anhydride), chlorobridge anhydride (chlorendic acid anhydride), tetrabromophthalic anhydride (tetrabromophthalic acid anhydride), polyazelaic anhydride (polyazelaic acid anhydride), fumaric anhydride (fumaric acid anhydride) itaconic anhydride (itaconic acid anhydride), acrylic anhydride (acrylic acid anhydride), and methacrylic anhydride (methacrylic acid anhydride). Anhydrides having three functional groups such as, but not limited to: trimellitic anhydride (trimellitic acid anhydride). Anhydrides having at least four functional groups such as, but not limited to: at least one selected from the group consisting of Jiao Midan anhydride (pyromellitic acid anhydride), benzophenone-tetracarboxylic anhydride (benzophenone-tetracarboxylic acid anhydride), and ethylene glycol bis-trimellitic anhydride (ethylene glycol bis-trimellitate acid anhydride). Anhydrides having at least six functional groups such as, but not limited to: alkylstyrene-maleic anhydride copolymer (alkylstyrene-maleic anhydride copolymers).

One of the important characteristics of the compound of the present invention is that the compound has an EO (ethylene oxide)/PO (propylene oxide) block copolymer, wherein the EO segment has hydrophilicity, so that the compatibility of the compound with water can be improved, and the PO segment has lipophilicity, so that the compatibility of the compound with epoxy resin can be improved. In a preferred embodiment, the compound is formed by reacting an anhydride, such as trimellitic anhydride (TMA), hexahydrophthalic anhydride (HHPA), with an "EO/PO block copolymer compound"; the foregoing "block polymeric compounds having EO/PO" are for example but not limited to: a compound having an EO-PO-EO block copolymer or a compound having a PO-EO-PO block copolymer; the molecular weight of the block copolymer having EO/PO may be, but is not limited to, 2500-20000, preferably 3500-15000, more preferably 8000-12500; the viscosity of the compound of the present invention for its backend application may be adjusted by selecting the appropriate molecular weight of the EO/PO block copolymer compound according to the desired application of the compound of the present invention. In another preferred embodiment, the compound is formed by reacting an anhydride (e.g., trimellitic anhydride (TMA), hexahydrophthalic anhydride (HHPA)), a compound having EO/PO block copolymers, and a polyethylene glycol (having EO segments), the polyethylene glycol having a molecular weight of 1000-10000, preferably 3000-8000.

The block copolymer having EO-PO-EO can be represented by the following formula (VIII), wherein x, y, and z can be: x=68, y=34, z=68 (2:1:2), such as Genapol PF80 (molecular weight mw=8000; available from Clariant company); x=5, y=36, z=5 (0.14:1:0.14), such as Genapol PF20 (mw=2500; available from Clariant company); x=100, y=65, z=100 (1.5:1:1.5), such as Pluronic F127 (mw=12500; available from BASF corporation); x=71, y=30, z=71 (2.4:1:2.4), such as Pluronic PE6800 (mw=8000; available from BASF corporation).

The aforementioned block copolymer having PO-EO-PO may be represented by the following formula (IX), wherein x, y, and z may be: x=27, y=6, z=27 (1:0.22:1), such as Pluronic RPE3110 (mw=3500; available from BASF).

The polyethylene glycol may be represented by the following formula (X), wherein n=22 (mw=1000; e.g. polyglykol 1000, available from Clariant) or n=180 (mw=8000; e.g. polyglykol8000, available from Clariant).

Suitable such compounds are of the general formula (I), and may have at least one of the following structures (II) to (VII):

One of the applications of the compounds of the present invention is as a surfactant which is added as an emulsifier to an epoxy resin to form an epoxy resin composition (particularly an aqueous epoxy resin composition), and since the compounds of the present invention wherein EO segments have hydrophilicity, the compatibility of water with the compounds is improved, so that an epoxy resin composition comprising the compounds has high solubility in water; furthermore, as the PO chain segment of the compound has lipophilicity, the compatibility of the compound and epoxy resin is improved, and the corrosion resistance of the epoxy resin composition is further improved.

The aqueous epoxy resin composition of the present invention is a resin composition suitable for formulation in water or a mixture of water and a water-soluble solvent, such as, but not limited to: as suspensions, emulsions, microemulsions, and the like. The epoxy resin in the aqueous epoxy resin composition may be any known epoxy resin such as, but not limited to: BPA epoxy resin (epoxy resin obtained from epichlorohydrin or beta-methyl epichlorohydrin and bisphenol a, bisphenol F or bisphenol sulfone); polyglycidyl ethers of polyhydric alcohols (e.g., phenol novolac polyglycidyl ether resins and cresol novolac polyglycidyl ether resins); polyglycidyl ethers of alkylene oxide adducts such as bisphenol A, polypropylene glycol, 1, 6-hexanediol, trialkyl methylpropane and glycerin; polyglycidyl ethers of polycarboxylic acids such as adipic acid, phthalic acid and dimer acid; polyglycidyl amines.

As used herein, "epoxide equivalent weight" refers to the weight in grams of an epoxy resin containing 1 mole epoxide equivalent. The epoxy equivalent weight may be measured or monitored by any method known in the art, for example: pyrolysis gas chromatography, gel permeation chromatography, spectroscopic analysis (such as infrared, near infrared and nuclear magnetic resonance spectroscopy) and titration methods. The epoxy resin has a proper epoxy equivalent range, if the epoxy equivalent is too high, the softening point of the resin is also high, and the film forming property of the epoxy resin is poor when the epoxy resin is applied to a coating subsequently, and more solvent is needed to be added to improve the film forming property; in contrast, if the epoxy equivalent is too low, the crosslinking density of the resin cured is high, and the hardness of the coating film to be applied later is high, so that the flexibility and impact resistance are lowered. In a preferred embodiment, the epoxy resin has an epoxy equivalent weight of 150 to 3500, such as, but not limited to: 150. 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950, 2000, 2050, 2100, 2150, 2200, 2250, 2300, 2350, 2400, 2450, 2500, 2550, 2600, 2650, 2700, 2750, 2800, 2850, 2900, 2950, 3000, 3050, 3100, 3150, 3200, 3250, 3300, 3350, 3400, 3450, or 3500. In a more preferred embodiment, the epoxy resin has an epoxy equivalent weight of 150 to 650, such as, but not limited to: 150. 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, or 650. In another preferred embodiment, the epoxy resin has an epoxy equivalent weight of 500 to 650, such as but not limited to: 500. 502, 504, 506, 508, 510, 512, 514, 516, 518, 520, 522, 524, 526, 528, 530, 532, 534, 536, 538, 540, 542, 544, 546, 548, 550, 552, 554, 556, 558, 560, 562, 564, 566, 568, 570, 572, 574, 576, 578, 580, 582, 584, 586, 588, 590, 592, 594, 596, 598, 600, 602, 604, 606, 608, 610, 612, 614, 616, 618, 620, 622, 624, 626, 628, 630, 632, 634, 636, 638, 640, 642, 644, 646, 648 or 650.

In the aqueous epoxy resin composition, the compound/the epoxy resin has a ratio ranging from 5% to 15%, such as, but not limited to: 5% to 15%, 5% to 14%, 5% to 13%, 5% to 12%, 5% to 11%, 5% to 10%, 5% to 9%, 5% to 8%, 5% to 7%, 5% to 6%, 6% to 15%, 6% to 14%, 6% to 13%, 6% to 12%, 6% to 11%, 6% to 10%, 6% to 9%, 6% to 8%, 6% to 7%, 7% to 15%, 7% to 14%, 7% to 13%, 7% to 12%, 7% to 11%, 7% to 10%, 7% to 9%, 7% to 8%, 8% to 15%, and 8% to 14%, 8% to 13%, 8% to 12%, 8% to 11%, 8% to 10%, 8% to 9%, 9% to 15%, 9% to 14%, 9% to 13%, 9% to 12%, 9% to 11%, 9% to 10%, 10% to 15%, 10% to 14%, 10% to 13%, 10% to 12%, 10% to 11%, 11% to 15%, 11% to 14%, 11% to 13%, 11% to 12%, 12% to 15%, 12% to 14%, 12% to 13%, 13% to 15%, 13% to 14%, or 14% to 15%.

The coating composition of the present invention is prepared by dispersing the aqueous epoxy resin composition in a solvent, preferably water or a mixture of water and a water-soluble solvent. In a preferred embodiment, the coating composition may further comprise an additive selected from the group consisting of pigments, dyes, defoamers, anti-flash rust agents, rheology modifiers, fillers, extenders, corrosion inhibitors, dispersants, and combinations thereof. In another preferred embodiment, the coating composition further comprises a curing agent. In other words, the aqueous epoxy resin composition of the present invention can be mixed with a curing agent and any additives (e.g., dyes, colorants, defoamers, etc.) to obtain the coating composition of the present invention, which can be applied to a substrate to form a coating.

The terms "pigment" and "dye" as used herein refer to any material that changes the color of reflected or transmitted light due to the use of wavelength selectivity. Dyes are soluble compounds, whereas pigments are usually solid particles. Pigments and dyes may include organic and inorganic. In some embodiments, the pigment used to formulate the aqueous epoxy coating composition is selected from one or more of: ultramarine violet (e.g., sodium silicate and aluminosilicate containing sulfur), han violet (BaCuSi) ₂ O ₆ ) Cobalt pigments (e.g.: cobalt violet (e.g., cobalt orthophosphate)), manganese pigments (e.g.: manganese violet (NH) ₄ MnP ₂ O ₇ ) Jin Yanliao (for example: purple gold (such as gold nanoparticle suspended in tin dioxide, ultramarine-PB 29), sodium silicate sulfate (Na) _8-10 Al ₆ Si ₆ O ₂₄ S ₂ -4), bosch blue (e.g.: ground celadon stone), cobalt blue-PB 28, sky blue-PB 35, egypt blue (e.g.: calcium copper silicate, caCuSi ₄ O ₁₀ ) Han blue (e.g.: baCuSi ₄ O ₁₀ ) Blue copper ore (e.g.: copper carbonate hydroxide, cu ₃ (CO ₃ ) ₂ (OH) ₂ ) Prussian blue-PB 27 (e.g.: iron hexacyanoferrate Fe ₇ (CN) ₁₈ ) Yttrium indium manganese Blue (YInMn Blue), manganese Blue (e.g.: barium manganate (VI) sulfate compound), cadmium green, chromium oxide (e.g.: cr (Cr) ₂ O ₃ ) Chrome oxide green-PG 17, viridian-PG18 (e.g.: cr (Cr) ₂ O ₃ 〃H ₂ O), cobalt green (e.g.: coZnO ₂ ) Malachite (e.g.: cu (Cu) ₂ CO ₃ (OH) ₂ ) Scheelee's Green), copper arsenite (e.g.: cuHAsO ₃ ) Smectite (Green earth/tere verte/Verona Green, K [ (Al, feIII), (FeII, mg))](AlSi ₃ ,Si ₄ )O ₁₀ (OH) ₂ ) Estrin (e.g.: as As ₂ S ₃ ) Primula yellow-PY 184 (e.g.: biVO (BiVO) ₄ ) Cadmium yellow-PY 37 (e.g.: cdS), chrome yellow-PY 34 (e.g.: crO (CrO) ₄ ) Aureolin or cobalt yellow-PY 40 (e.g.: k (K) ₃ Co(NO ₂ ) ₆ ) Ocher (Yellow Ochre) -PY43 (e.g.: fe (Fe) ₂ O ₃ .H ₂ O), napples Yellow (Naples Yellow) -PY41, lead tin Yellow (e.g.: pbSnO ₄ Or Pb (Sn, si) O ₃ ) Titanium yellow-PY 53, mosaic gold (e.g.: snS (SnS) ₂ ) Zinc yellow-PY 36 (e.g.: znCrO ₄ ) Cadmium orange-PO 20 (e.g.: cadmium selenide sulfide), chromium orange (e.g.: pbCrO ₄ +pbo), realgar (e.g.: as As ₄ S ₄ ) Cadmium red-PR 108 (e.g.: cd (cadmium sulfide) ₂ SSe), red blood (Sanguine), cast Mortum, indian Red (Indian Red), venetian Red (Venetian Red), oxide Red (Oxide Red) -PR102, ocherPR102 (e.g. anhydrous Fe) ₂ O ₃ ) Jiao Xien (burn Sienna) -PBr7, red lead (Minium pigment, for example: pb ₃ O ₄ ) Vermilion (Vermilion) -PR106 (e.g.: cinnabar), mercury sulfide (HgS), clay pigment (e.g.: iron oxide), brown (Raw unit) -PBr7, and burn brown (burn unit, for example: fe (Fe) ₂ O ₃ +MnO ₂ +nH ₂ O+Si+Al ₂ O ₃ The method comprises the steps of carrying out a first treatment on the surface of the When calcined (heated), it is called Jiao Zong (burn unit), and has a more intense color), green ocher (Raw Sienna) -PBr7 (e.g.: limonite clay), carbon Black-PBk 7, ivory Black (PBk 9), vine Black (Vine Black) -PBk8, lamp Black (Lamp Black) -PBk6, iron pigments, mars Black) -PBk11 (e.g.: fe (Fe) ₃ O ₄ ) Manganese dioxide (e.g.: mnO (MnO) ₂ ) Titanium black (for example: ti (Ti) ₂ O ₃ ) Antimony white (e.g.: sb (Sb) ₂ O ₃ ) Barium sulfate-PW 5 (e.g.: baSO (Baso) ₄ ) Lithopone (Lithopone, e.g. BaSO) ₄ * ZnS), white lead (Cremnitz White) -PW1 (e.g.: (PbCO) ₃ ) ₂ 〃Pb(OH) ₂ ) Titanium white-PW 6 (e.g.: tiO (titanium dioxide) ₂ ) Zinc white-PW 4 (e.g.: znO), 1, 2-dihydroxyanthraquinone, anthoxanthin (anthoxan), arylyellow (aryl yellow), azo dyes, bislin (Bilin, for example: bilirubin bilirubibin), soot, bone char, carmine (e.g.: aluminum carminate), diaryl (diaryl) pigments, dibromoanthracene xanthone (dibroantanthrone), dragon's blood, gamboge (Gamboge), indian yellow (e.g.: magnesium euxanthate and calcium euxanthate), indigo dye color (Indigo dye, for example: 2,2' -Bis (2, 3-dihydro-3-oxorindolide, indigo Indigotin), naphthol AS, (Naphthol AS, e.g., 3-hydroxy-N-phenylnaphthalene-2-carboxamide), naphthol Red (Naphthol Red, e.g., 4- (2- (4-carbamoylphenyl) hydrazono) -N- (2-ethoxyphenyl) -3-oxo-3, 4-dihydronaphthalene-2-carboxamide), eyepigment (ommochrome.g., tryptophan, metabolites through kynurenine and 3-hydroxykynurenine), perinone, phthalocyanine blue BN, phthalocyanine green G, pigment violet 23, pigment yellow 10, pigment yellow 12, pigment yellow 13, pigment yellow 16, pigment yellow 81, pigment yellow 83, pigment yellow 139, pigment yellow 185, quinacridone Rosea madder (e.g., alizarin and rhodopsin), ryene dyes, and taylor violet (e.g., 6' -dibromoindigo). In some embodiments, the pigment is titanium dioxide (e.g., tiO ₂ )。

As used herein, "defoamer" refers to a chemical additive that reduces and hinders foam formation. The additive may be one or more compound formulations. The defoamer comprises

And

Purchased from BASF, for example: />

MO2134、/>

MO 2150、/>

NO 2335, FOAMSTAR ED 2521, FOAMSTAR ED 2522, FOAMSTAR ED 2523, FOAMSTAR NO 2306, FOAMSTAR SI 2210, FOAMSTARSI 2213, FOAMSTAR SI 2216, FOAMSTAR SI 2250, FOAMSTAR SI 2280, FOAMSTAR SI 2293, FOAMSTAR ST 2438, and FOAMSTAR ST 2454. In some embodiments, the defoamer is FOAMSTAR->

ST2438。

As used herein, a "rheology modifier (rheology modifier)" is a compound or composition added to adjust the rheology of a formulation. For example: the rheology modifier can improve sag resistance of the coating by a rapid but controlled viscosity increase after application, improving transportability and storage of the coating by helping to prevent sedimentation of the pigment or other solids in the formulation. In some embodiments, the rheology modifier may be inorganic, e.g : clay, fumed silica (fused silica) and specialty clays (e.g., sepiolite, attapulgite and smectite). In some embodiments, the rheology modifier may be organic, for example: cellulose materials and synthetic materials (e.g., hydrophobically modified polyurethanes, hydrophobically modified polyethers, alkali-swellable emulsions, castor oil thixotropic agents). In some embodiments, the rheology modifier is used

DE, a highly synergistic, ultra-dispersible powdered lithium bentonite clay.

As used herein, a "filler" or "extender" may be any suitable material, such as: any dry and inert (e.g., chemically inert) material. The addition of filler may be for various reasons, for example, in some embodiments, to reduce cost, to change the strength, weight, or appearance of the blank, or to make the resin coating more practical before or after hardening. In some embodiments, the filler may be selected from the group consisting of: microspheres (e.g. hollow ceramic microspheres, high strength hollow spherical glass-hard-inert silicate

(Tolsa USA inc.), perlite derived microspheres

(La Pin, noble International SA, france), perlite microspheres, plastic microspheres (e.g., phenolic, amino, and vinyl microspheres), expandable microspheres (e.g., as described in U.S. Pat. No.3615972, incorporated herein by reference, EXPANCEL) ^TM Microspheres (akzo nobel, usa), calcium carbonate, limestone sand, marble powder, magnesium silicate (e.g., talc)), slate powder, silica (e.g.,>

is->

Fumed silica (Cabot Corp Co., USA), colloidal silica, aluminum hydroxide, alumina, barium sulfate (BaSO) ₄ For example, blanc fix Micro (germany, sachtleben Chemie corporation)), metal powders (e.g., brass, copper, aluminum, iron, and bronze), fibrous fillers, polyethylene fibers (e.g., available from>

Poly Fiber II from Development Corp), glass fibers (e.g., ground glass fibers, chopped glass fibers), carbon fibers (e.g., milled carbon fibers), walnut shell flour, hickory shell flour, wood flour, corn cob flour, rice hull flour, ground rubber, ground leather, cellulose (e.g., cotton fibers, sisal, flax, hemp and other natural fibers), and the like. In some embodiments, the filler or the extender comprises talc and barium sulfate.

As used herein, "corrosion inhibitor" refers to an ingredient (e.g., a chemical or composition) that, when added to a formulation, reduces the corrosion rate of the material to which it is applied. For example: the corrosion inhibitor reduces corrosion conditions on the metal surface when a fluid containing the corrosion inhibitor is in contact with the surface. As used herein, a "rust inhibitor" is a corrosion inhibitor that, for example, may be used to prevent corrosion of iron surfaces. In some embodiments, the inhibitor is selected from inorganic compounds, such as: na, K, zn, ca, sr, ba, al, mg, pb, cr, fe or a combination of these anionic and cationic species. In some embodiments, the inhibitor is an organic compound, such as a thiol, and derivatives of dithiocarbonic acid, dithiocarbamic acid, and dithiophosphoric acid. Some examples of organic inhibitors include nitrogen-containing heterocyclic mercapto (N-containing heterocyclic mercapto) derivatives (e.g., 2-mercaptobenzothiazole, MBT); amines (e.g., hexamine, phenylenediamine, dimethylethanolamine, derivatives thereof, etc.); ascorbic acid; and benzotriazole. In some embodiments, mixtures and reaction products of inorganic and organic inhibitors, such as Zn (MBT) 2, as described in U.S. Pat. No. 6139610, which is incorporated herein by reference. In some embodiments, the corrosion inhibitor is zinc phosphate or a zinc organic complex, such as:

FA 579 (Elementis plc company, usa).

As used herein, "dispersing/dispersing agent" refers to a non-surface active compound or surface active compound added to a suspension (e.g., colloid) to improve particle separation and prevent sedimentation (settling), agglomeration (agglomeration), accumulation (agglomeration), and flocculation (flocculation). The dispersant may be selected according to the formulation and may include compounds that provide particle steric stabilization or electrostatic stabilization in the formulation. For example, in some embodiments, the dispersant is a nonionic, anionic, or cationic surface-active polymer or surfactant, such as: quaternary ammonium salts and alkyl polyamines (cations); polyacrylic acid and sulfonated organic substances (anions); nonionic or nonionic-based materials having hydrophilic groups (e.g., ethylene oxide and propylene oxide units). In some embodiments, the dispersant is a polyacrylic acid, for example:

CX 4320 (BASF corporation, germany).

As used herein, "curing" refers to toughening or hardening of a polymeric material via cross-linking of the polymer chains, which may be caused by electron beams, UV radiation, heat, chemical additives, or combinations thereof. As used herein, "curing agent" refers to a chemical compound or composition that is added to a resin composition to toughen or harden the composition (e.g., when it is applied to a surface). In some embodiments, the curing agent is an aliphatic amine, aromatic amine, tertiary amine, primary amine, polyamine epoxy resin adduct, ketimine, polyamide resin, imidazole, polythiol, polysulfide resin, aromatic anhydride, cycloaliphatic anhydride, aliphatic anhydride, latent curing agent (latent curing agen)t) and one or more UV/light curing agents. Without limitation, a compound selected from the following may be used in some embodiments of the formulations described herein: diphenyliodonium hexafluorophosphate (diphenyliodonium hexafluorophosphate), triphenylsulfonium hexafluorophosphate (triphenylsulfonium hexafluorophosphate), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, N-aminoethylpiperazine, menthanediamine, isophoronediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, piperidine, N, N-dimethylpiperidine, triethylenediamine, 2,4, 6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2-methylimidazole, 2-acetic-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, phthalic anhydride, trimellitic anhydride, jiao Midan anhydride, benzophenone carboxylic anhydride, ethylene glycol bis-trimellitate, glycerol trimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, alkylstyrene-maleic anhydride copolymer, chlorodicarboxylic anhydride, polyazelaic anhydride, BF ₃ -amine complexes, organic-acid hydrazides and dicyandiamides. In a preferred embodiment, the curing agent is a polyamine adduct, such as: EPIKURE ^TM Curing agent 8530-W-75 (Hexion Inc. of Columbus, ohio). In a preferred embodiment, the curing agent which may be further added to the coating composition of the present invention may be an alkaline curing agent, for example, comprising: aliphatic polyamines, cycloaliphatic polyamines, mannich bases (Mannich bases), amine-epoxy adducts, polyamide polyamines, and liquid aromatic polyamines; examples of the aforementioned curing agent are JOINTMINE #4160 and EPIKURE curing agent 8530-W-75 (HEXION Co.). The coating composition may be applied to a substrate by spraying, brushing, curtain coating, air knife coating, and other coating forming techniques. After drying, the cured coating film has excellent corrosion resistance and water resistance.

The coating composition has a solids content, i.e., a solids content left after drying to a constant weight. In a preferred embodiment, the solids content of the coating composition is 50% to 60%, such as, but not limited to: 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5%, 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59%, 59.5% or 60%. In a more preferred embodiment, the solids content of the coating composition is 55% to 60%, such as, but not limited to: 55%, 55.1%, 55.2%, 55.3%, 55.4%, 55.5%, 55.6%, 55.7%, 55.8%, 55.9%, 56%, 56.1%, 56.2%, 56.3%, 56.4%, 56.5%, 56.6%, 56.7%, 56.8%, 56.9%, 57%, 57.1%, 57.2%, 57.3%, 57.4%, 57.5%, 57.6%, 57.7%, 57.8%, 57.9%, 58, 58.1%, 58.2%, 58.3%, 58.4%, 58.5%, 58.6%, 58.7%, 58.8%, 58.9%, 59%, 59.1%, 59.2%, 59.3%, 59.4%, 59.5%, 59.6%, 59.7%, 59.8%, 59.9% or 60%.

The coating composition has a viscosity. In a preferred embodiment, the viscosity ranges from about 130cps/25 ℃ to about 18000cps/25 ℃, such as, but not limited to: about 130cps/25 ℃ to about 1000cps/25 ℃, about 130cps/25 ℃ to about 5000cps/25 ℃, about 130cps/25 ℃ to about 10000cps/25 ℃, about 130cps/25 ℃ to about 15000cps/25 ℃, about 130cps/25 ℃ to about 18000cps/25 ℃, about 500cps/25 ℃ to about 1000cps/25 ℃, about 500cps/25 ℃ to about 5000cps/25 ℃, about 500cps/25 ℃ to about 10000cps/25 ℃, about 500cps/25 ℃ to about 15000cps/25 ℃, about 500cps/25 ℃ to about 18000cps/25 ℃, about 3000cps/25 ℃ to about 5000cps/25 ℃, about 3000cps/25 ℃ to about 7000cps/25 ℃, about 3000cps/25 ℃ to about 10000/25 ℃, about 3000cps/25 ℃ to about 15000cps/25 ℃, about 3000cps/25 ℃ to about 10000cps/25 ℃, about 180 cps/25 ℃ to about 180 cps/25 ℃, or about 180/00 cps/25 ℃ to about 18000cps/25 ℃, etc. In a preferred embodiment, the viscosity ranges from about 4000cps/25 ℃ to about 17000cps/25 ℃, such as, but not limited to: about 4000cps/25 ℃ to about 7000cps/25 ℃, 4000cps/25 ℃ to about 10000cps/25 ℃, 4000cps/25 ℃ to about 13000cps/25 ℃, 4000cps/25 ℃ to about 17000cps/25 ℃, 7000cps/25 ℃ to about 10000cps/25 ℃, 7000cps/25 ℃ to about 14000cps/25 ℃, 7000cps/25 ℃ to about 17000cps/25 ℃, 9000cps/25 ℃ to about 10000cps/25 ℃, 9000cps/25 ℃ to about 14000cps/25 ℃, 9000cps/25 ℃ to about 17000cps/25 ℃, or 10000cps/25 ℃ to about 17000cps/25 ℃, etc. In another preferred embodiment, the viscosity is greater than 600cps/25 ℃.

As used herein, "water-soluble solvent" refers to any solvent that is inactive to the components of the present invention. Specific examples include: esters, alcohols, glymes, propylene glycol monomethyl and mono-t-butyl ethers of propylene glycol, and ketones. In some embodiments, the water may include deionized and/or distilled water. In some embodiments, the solvent is selected from Propylene Glycol Monomethyl Ether (PGME), methanol, ethanol, glycol ethers (e.g., diethyl, t-butyl, cyclic ethers), glycols, ketones (e.g., acetone), and mixtures thereof. In some embodiments, the aqueous epoxy resin contains little volatile organic solvents (e.g., less than 1000ppm, less than 100ppm, less than 10ppm, less than 1 ppm) such as aliphatic hydrocarbons, ethyl acetate, glycol ethers, and acetone.

In the application test of the present invention, "hardness" as used herein refers to a measure of the resistance to localized plastic deformation caused by mechanical indentation or abrasion. Hardness can be measured using different methods depending on the material. For example: the Mohs scale is based on the ability of a sample of natural minerals to cause significant scratching of another mineral, while the hardness of polymers (rubber, plastic) is typically expressed in terms of Shore hardness (Shore hardness) and is measured using a durometer that measures the depth of an indentation made on a material by a known force on a standardized presser foot. Another hardness scale is based on the scratch of the surface with a pencil described in ASTM test method D3363-00 (pencil tested film hardness standard test method) and provides a hardness, for example: 9B, 8B, 7B, 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H (9B is the softest, 9H is the hardest) from soft to hard hardness. In the foregoing ASTM test methods, a test sample (e.g., an applied test piece) is placed on a firm horizontal surface. The pencil, corrected to one of the hardnesses (e.g., 9B to 9H), is held firmly on the film under test at a 45 deg. angle and the test point is spaced away from the operator, pushing the pencil away from the operator at a 6.5-mm (1/4-in.) stroke. The test procedure was started with the hardest pencil and continued to test on the hardness scale until the pencil failed to cut or dig into the film. The pencil hardness is selected from the hardest pencil that does not scratch the surface of the sample. In some embodiments, the coating compositions of the present invention may form coatings having a hardness greater than 9B (e.g., greater than 8B, greater than 7B, greater than 6B, greater than 5B, greater than 4B, greater than 3B, greater than 2B, greater than B).

As used herein, "adhesion" refers to the attractive force that causes two different substances to join, e.g., coating adhesion refers to the minimum force required to fully attach a layer of coating resin formulation to a metal substrate. The coating which is durable and resistant to chemical corrosion has a greater coating adhesion. Adhesion may be quantified by ASTM test method D3359-09, which provides a minimum to maximum adhesion rating from grade 0, grade 1, grade 2, grade 3, grade 4, or grade 5, respectively. The method evaluates the adhesion of the coating film and the metal substrate by applying and removing pressure sensitive adhesive tapes on the cuts created in the film. The test methods include two kinds of test methods, namely test method A and test method B. In test a, an X-shaped incision was made from the film to the substrate, and a pressure-sensitive adhesive tape was applied over the incision, after which the pressure-sensitive adhesive tape was removed and the adhesion was evaluated qualitatively on a scale of 0 to 5. For test a, the adhesion rating is: 5A is no peeling or removal; 4A is peeling or removing along the incision or trace at the intersection thereof; 3A is a staggered removal along the incision, up to 1.6mm (1/16 in.); 2A is a staggered removal along most incisions, up to 3.2mm (1/8 in.); 1A is the majority of the X-shaped area under the tape is removed; and 0A removing beyond the X-type region. In test B, a lattice pattern having 6 or 11 cuts in each direction was produced from the film to the substrate, then a pressure-sensitive adhesive tape was applied on the lattice pattern, and then the pressure-sensitive adhesive tape was removed. The evaluation of the adhesion is compared via description and illustration. For test B, the adhesion was graded as: 5B is that the edges of the notch are completely smooth, and no square block with any grid pattern falls off; 4B is that a small piece of coating falls off at the crossing point, and the affected area is less than 5%;3B is that the small pieces of coating are separated along the intersections of the edges and the cuts, and the affected area is 5% to 15% of the lattice pattern; 2B is the partial flaking of the coating along the edges and squares, the affected area being 15% to 35% of the lattice pattern; 1B is that the coating is peeled off in large pieces along the edges of the notch, the whole square is peeled off, and the affected area is 35 to 65 percent of the grid pattern; and 0B is a peel and separate condition worse than 1 level. In some embodiments, the adhesion of the present invention is greater than 5B using test method ASTM D3359-09-test method B.

As used herein, "corrosion" refers to the process of degrading a material. By metal, it is meant a reaction that converts the metal into a more chemically stable form, e.g., an oxide, hydroxide or sulfide thereof. Corrosion is typically a gradual failure of the material, and because the process is typically slow (e.g., takes months or years), accelerated tests are typically used to evaluate corrosiveness or corrosion resistance. Salt spray testing (salt spray or salt fog) is a commonly used corrosion test method for inspecting the corrosion resistance of materials and surface coatings. Typically, the material to be tested is a metallic (although stone, ceramic and polymer may also be tested) surface coating that is intended to provide a degree of corrosion protection to the underlying metal. The salt spray test is an accelerated corrosion test that produces a corrosive attack on a sample of the coating to evaluate (principally relative to) the suitability of the coating as a protective coating. The appearance of corrosion products (rust or other oxides) was evaluated after a predetermined time interval. The duration of the test depends on the corrosion resistance of the coating; in general, the more corrosion resistant the coating, the longer the test time for corrosion/rust to occur. There are several standard salt spray tests, including ASTM test method B117, other important relevant standards are ISO9227, JIS Z2371 and ASTM G85. Salt spray tests are subjective tests and depend on the particular test and on different ratings of different test environments (e.g., different laboratories). For example, the test may evaluate the number of corrosion spots, the amount of pitting, the loss of coating material, color discoloration/change, and quality change (e.g., quality loss due to material loss, or quality increase due to oxidation) of the test sample. If it is desired to determine the corrosion development of the abraded area in the coating, the test may further comprise providing a cut from the coating to the substrate as described in ASTM test method D1654. Thus, the test may be a comparative test of corrosion resistance between different coating compositions, wherein a first coating on a substrate may be rated as being better (e.g., improved, more corrosion resistant, less corroded) than a second coating or a third coating on the same substrate if there are fewer corrosion points, less pitting, less coating loss, less color discoloration, less quality change, less other signs of corrosion, or a combination of these criteria on the first coated substrate than on the second coated substrate or the third coated substrate. The grading of corrosion resistance may be, for example: good, normal or bad. In some embodiments, the corrosion resistance of a coating (or film) formed using a coating composition according to the present invention is better than the corrosion resistance of a coating that does not use one or more of these components. In a preferred embodiment, the coating composition has a weight loss of less than about 0.36 grams as measured by salt spray testing (ASTM B117). In a more preferred embodiment, the coating composition has a weight loss of less than about 0.17 grams as measured by salt spray testing (ASTM B117).

The invention is illustrated in more detail by the following exemplary examples. While exemplary embodiments are disclosed herein, it should be understood that they are presented by way of illustration of the invention, and not limitation.

Examples (example)

EXAMPLE 1 Synthesis of Compound S1.1, preparation of aqueous epoxy resin composition S1.2

As shown in fig. 1A and 1B, trimellitic anhydride (TMA, formula (XI) below) was mixed with a polymer having EO-PO-EO block copolymerization (molecular weight mw=8000; trade name Genapol PF80 from Clariant company) and polyethylene glycol (mw=8000; trade name polyglykol 8000 from Clariant company) and reacted with Titanium (IV) isopropoxide, TPT, as a catalyst. The reaction was stirred and maintained under vacuum until the acid value was no longer reduced, to obtain compound S1.1 having the structure of formula (II) as described above.

Bisphenol a diglycidyl ether (BE 188, vinca resin works inc.), bisphenol a (BPA) and polyetheramine (PEA,

m-2070, henschel chemical Co., ltd.) and after stirring and heating to about 90℃the catalyst was added. Heating and reacting, adding the compound S1.1 as an emulsifying agent, adding epoxidized oil (such as epoxidized soybean oil, epoxidized soybean oil and ESBO), heating and reacting, adding alcohol ether solvent (such as propylene glycol methyl ether), cooling to 80 ℃, and adding pure water to obtain the product waterborne epoxy resin composition S1.2.

EXAMPLE 2 Synthesis of Compound S2.1, preparation of aqueous epoxy resin composition S2.2

As shown in fig. 2A and 2B, compound S2.1 was synthesized using the ingredients and methods previously described in example 1, except that the starting ingredients were reacted using different block-copolymerized polymers having EO-PO-EO (mw=12500; available from BASF company under the trade name Pluronic F127) to increase molecular weight. The compound S2.1 finally obtained by the synthesis reaction has the structure of formula (III) as described above.

Next, an aqueous epoxy resin composition S2.2 was prepared using the ingredients and methods previously described in example 1, except that the aforementioned compound S2.1 was added as an emulsifier in the middle of the reaction instead of S1.1. Finally, the reaction product aqueous epoxy resin composition S2.2 is obtained.

EXAMPLE 3 Synthesis of Compound S3.1, preparation of aqueous epoxy resin composition S3.2

As shown in fig. 3A and 3B, compound S3.1 was synthesized using the ingredients and methods previously described in example 1, except that the starting ingredients were reacted using different EO-PO-EO block copolymer polymers (mw=2500; commercially available from Clariant corporation under the trade name Genapol PF 20) and polyethylene glycols of different molecular weights (mw=1000; commercially available from Clariant corporation under the trade name polyglykol 1000) to reduce the molecular weight. The compound S3.1 finally obtained by the synthesis reaction has the structure of formula (IV) as described above.

Next, an aqueous epoxy resin composition S3.2 was prepared using the ingredients and methods previously described in example 1, except that the aforementioned compound S3.1 was added as an emulsifier in the middle of the reaction instead of S1.1. Finally, the reaction product aqueous epoxy resin composition S3.2 is obtained.

EXAMPLE 4 Synthesis of Compound S4.1, preparation of aqueous epoxy resin composition S4.2

As shown in fig. 4A and 4B, compound S4.1 was synthesized using the ingredients and methods previously described in example 1, except that the starting ingredients were reacted using different block-copolymerized polymers having EO-PO-EO (mw=8000; commercially available from BASF corporation under the trade name Pluronic PE 6800) and no polyethylene glycol was added. The compound S4.1 finally obtained by the synthesis reaction has the structure of formula (V) as described above.

Next, an aqueous epoxy resin composition S4.2 was prepared using the ingredients and methods previously described in example 1, except that the aforementioned compound S4.1 was added as an emulsifier in the middle of the reaction instead of S1.1. Finally, the reaction product aqueous epoxy resin composition S4.2 is obtained.

EXAMPLE 5 Synthesis of Compound S5.1, preparation of aqueous epoxy resin composition S5.2

As shown in fig. 5A and 5B, compound S5.1 was synthesized using the ingredients and methods previously described in example 1, except that the starting ingredients were reacted using a polymer having PO-EO-PO block copolymers (mw=3500; available from BASF company under the trade name Pluronic RPE 3110). The compound S5.1 finally obtained by the synthesis reaction has the structure of formula (VI) as described above.

Next, an aqueous epoxy resin composition S5.2 was prepared using the ingredients and methods previously described in example 1, except that the starting ingredients bisphenol a diglycidyl ether (BE 188) and bisphenol a were changed to bisphenol a epoxy resin (available from vinca resin factory, trade name BE 501) directly used, and the aforementioned compound S5.1 was added as an emulsifier instead of S1.1 in the middle of the reaction. That is, bisphenol a epoxy resin (BE 501) and Polyetheramine (PEA) were mixed, stirred and heated to about 90 ℃, and then a catalyst was added. Heating and reacting, adding the compound S5.1 as an emulsifying agent, adding epoxidized soybean oil, heating and reacting, adding propylene glycol methyl ether, cooling to 80 ℃, and adding pure water to obtain the product waterborne epoxy resin composition S5.2.

EXAMPLE 6 Synthesis of Compound S6.1, preparation of aqueous epoxy resin composition S6.2

As shown in fig. 6A and 6B, compound S6.1 was synthesized using the components and methods described previously in example 1, except that the starting components were reacted using different anhydrides, and in this example hexahydrophthalic anhydride (HHPA, formula (XII) below) was used, and the remaining components and steps were the same. The compound S6.1 finally obtained by the synthesis reaction has the structure of formula (VII) as described above.

Next, an aqueous epoxy resin composition S6.2 was prepared using the ingredients and methods previously described in example 1, except that the aforementioned compound S6.1 was added as an emulsifier in the middle of the reaction instead of S1.1. Finally, the reaction product aqueous epoxy resin composition S6.2 is obtained.

Comparative example-Synthesis of Compound C1.1, preparation of aqueous epoxy resin composition C1.2

As shown in fig. 7A and 7B, compound C1.1 was synthesized using the components and methods described previously in example 1, except that the starting components were reacted using a copolymer polymer having only EO segments, i.e., not EO/PO blocks, and the remaining components and steps were the same. That is, trimellitic anhydride was mixed with polyethylene glycol having only EO block (molecular weight mw=8000; trade name polyglykol 8000 from Clariant company), reacted with Titanium (IV) isopropoxide (TPT) as a catalyst, and stirred and kept reacting in a vacuum state until the acid value was not lowered any more, to obtain compound C1.1.

Next, an aqueous epoxy resin composition C1.2 was prepared using the ingredients and methods previously described in example 1, except that the aforementioned compound C1.1 was added as an emulsifier in the middle of the reaction instead of S1.1. The reaction product aqueous epoxy resin composition C1.2 was finally obtained.

EXAMPLE 7 coating composition

Coating compositions were prepared using the aqueous epoxy resin compositions from examples 1 to 6 and comparative example 1 (i.e., S1.2 to S6.2 and C1.2) described above. Table 1 shows the ingredients of parts A and B of the formulations used to prepare the coating compositions. This example is given as an example of the preparation of a white paint coating composition and is described below.

White color paste preparation: firstly adding a dispersing agent, a defoaming agent and an anti-flash rust agent into deionized water according to the formula amount, dispersing the additive in water, weighing all powder materials (containing no water-based rheology modifier Bentone DE) and adding the powder materials for three times, stirring and dispersing until the viscosity is reduced and the agglomerated particles of the powder materials are not visible after each section of adding, adding the next section of powder materials until the powder materials are completely filled, adding water for adjustment if the viscosity is too high and stirring is difficult, adding beads for grinding, wherein the heating temperature can reach 60 ℃, grinding for 20 to 30 minutes, adding 7g of Bentone DE aqueous solution (containing 86 percent of water and 14 percent of bentonite) after the process heating can reach 60 ℃, stirring uniformly in advance, and filtering to obtain white color paste.

Addition of the aqueous epoxy resin composition: according to calculation, 6g of one of the aqueous epoxy resin compositions S1.2, S2.2, S3.2, S4.2, S5.2, S6.2 or C1.2 is added to 10g of color paste, and the two are uniformly mixed to obtain white paint when the white paint is used, so that the A part of a coating composition is obtained.

And (3) adding a hardening agent: the hardener was hexin 8530 (n.v. =75%, amine hydrogen equivalent AHEW 100), the hardener was diluted to 80% with (meth) acrylate polymer (PMAc), a proper amount of the white paint was added, and the white paint and hardener were mixed and the viscosity was adjusted with PMAc to be sprayable. The coating compositions prepared are designated S1, S2, S3, S4, S5, S6 and C1, respectively.

Table 1: formulation of coating compositions

The physical properties of examples and comparative examples, which are designed with 55 to 56% solids and 600 to 620g/eq epoxy equivalent, are shown in Table 2:

table 2:

test 1-quick drying test

Samples were coated with each of the coating compositions S1, S2, S3, S4, S5, S6 and C1. It was allowed to cure at 60℃for 30 minutes. The samples were then tested for coating adhesion and hardness. The formulation used as the coating composition may have a range of hardness values that can be expressed in terms of its film hardness via ASTM D3363-00, the foregoing ASTM D3363-00 being a standard test method for film hardness by pencil testing. The films of the samples also exhibited cross-hatch adhesion (cross hatch adhesion) of at least 5B grade (according to ASTM D3359-09). Notably, the data as set forth in table 3 shows that the S1, S2, S4, and S5 coatings exhibit superior hardness compared to C1.

Table 3: quick drying test results ASTM D3359-09 and D3363-00

Test 2 Corrosion test

Samples were coated with each of the coating compositions S1, S2, S3, S4, S5, S6 and C1. Samples were run in triplicate and subjected to a 250 hour salt spray exposure according to ASTM test method B117. The average value of three tests for each coating layer showed good, ordinary and poor, and the quantitative weight loss was shown in table 4, and the results showed that the weight loss due to corrosion was higher (weight loss up to 0.367 g) in comparative example sample C1 as compared with examples S1 to S6. Further, fig. 8 shows, from left to right, individual results of the test pieces S1, S2, S3, S4, S5, S6, and C1, which were evaluated by observing the presence or absence of corrosion at the scribe line and the presence or absence of rust, bubble point, pinhole, crack, peeling, and the like, and the results show that the samples coated with S1, S2, S3, S4, S5, and S6 exhibited better corrosion resistance than C1.

Table 4: list of corrosion results

Project	Corrosion resistance	Weight loss (g)
			S1	Good quality	0.102
S2	Good quality	0.110
			S3	General	0.189
S4	Good quality	0.124
			S5	Good quality	0.132
S6	General	0.172
			C1	Difference of difference	0.367

In view of the foregoing, it is an object of the present invention to provide a novel compound having a surfactant function, which can be added to an epoxy resin composition as an emulsifier to enhance compatibility between water and an epoxy resin, so that an epoxy resin composition comprising the compound has high solubility in water. Accordingly, the present invention further provides an aqueous epoxy resin composition using water as a solvent, and a coating composition comprising the same, which can greatly reduce the content of Volatile Organic Compounds (VOCs), and a coating layer made using the aqueous epoxy resin composition improves surface characteristics, such as: high hardness, good adhesion, good corrosion resistance, and low VOC. On the other hand, the aqueous epoxy resin composition and the coating composition of the invention can adjust the viscosity range by selecting the compound with different molecular weights as an emulsifier according to different requirements of later application.

While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

1. An aqueous epoxy resin composition comprising:

(a) An epoxy resin; and

(b) A compound, wherein (b) has at least one structure selected from the group consisting of formulas (II) to (VII):

2. The aqueous epoxy resin composition according to claim 1, wherein the ratio of (b)/(a) ranges from 5% to 15%.

3. The aqueous epoxy resin composition according to any one of claims 1 to 2, wherein the epoxy resin has an epoxy equivalent weight of 150 to 3500.

4. The aqueous epoxy resin composition of claim 3, wherein the epoxy resin has an epoxy equivalent weight of 150 to 650.

5. The aqueous epoxy resin composition of claim 4, wherein the epoxy resin has an epoxy equivalent weight of 500 to 650.

6. A coating composition comprising the aqueous epoxy resin composition of any one of claims 1 to 5 dispersed in a solvent.

7. The coating composition of claim 6, further comprising at least one additive selected from the group consisting of pigments, dyes, defoamers, flash rust inhibitors, rheology modifiers, fillers, extenders, corrosion inhibitors, dispersants.

8. The coating composition of claim 6, further comprising a curing agent.

9. The coating composition of claim 6, wherein the coating composition has a solids content of 50% to 60%.

10. The coating composition of claim 6, wherein the coating composition has a viscosity in the range of 130cps/25 ℃ to 18000cps/25 ℃.

11. The coating composition of claim 6, wherein the coating composition has a viscosity in the range of 4000cps/25 ℃ to 17000cps/25 ℃.

12. The coating composition of claim 6, wherein the coating composition has a viscosity of greater than 600cps/25 ℃.

13. The coating composition of any one of claims 6 to 12, wherein the coating composition has a hardness of class B or greater as measured by a pencil test.

14. The coating composition according to any one of claims 6 to 12, wherein the coating composition has a degree of adhesion of class 5B after adhesion testing.

15. The coating composition of any one of claims 6 to 12, wherein the coating composition has a weight loss of less than 0.36 grams when subjected to a salt spray test.

16. The coating composition of any one of claims 6 to 12, wherein the coating composition has a weight loss of less than 0.17 grams when subjected to a salt spray test.